KR101533669B1 - Blue-colored composition for color filter, color filter and color display - Google Patents

Abstract

There is provided a blue coloring composition for use in the production of a color filter excellent in color characteristics, heat resistance, light resistance and solvent resistance. The blue coloring composition for a color filter contains a binder resin and a coloring agent. The colorant comprises a blue pigment and a salt formation product, and the salt formation product is formed from a compound having a xanthene acid dye and a cationic group.

Description

TECHNICAL FIELD [0001] The present invention relates to a blue coloring composition for a color filter, a color filter and a color display,

The present invention relates to a blue coloring composition for use in the manufacture of color filters, such as color displays and color imaging devices, a color filter with filter segments formed from the blue coloring composition, and a color display comprising the color filter. In addition, this blue coloring composition can be used for the production of cyan filter segments as well as blue filter segments.

The liquid crystal display has, for example, a structure in which a liquid crystal layer is sandwiched between a pair of polarizing plates. In such a liquid crystal display, the state of the polarized light transmitted through one of the polarizing plates is changed by using the orientation of the liquid crystal molecules, thereby controlling the amount of light transmitted through the other polarizing plate.

Display modes of the liquid crystal display include VA (Vertically Aligned) mode, IPS (In-Plane Switching) mode, OCB (Optically Compensated Bend) mode and TN (Twisted Nematic) mode. Of these, the TN mode is the mainstream.

In these liquid crystal displays, a color image can be displayed by providing a color filter on a polarizing plate. Recently, color liquid crystal displays have come to be used in various devices such as a television receiver and a monitor of a PC. For this reason, color filters are required to have high contrast and high definition, and a demand for a wide color reproduction area and high reliability is also increasing.

The color filter has a structure in which two or more filter segments different in color are arranged on a transparent substrate such as glass. Each filter segment is as fine as several microns to several hundred microns in width. Various shapes and arrangements of filter segments are possible, such as stripe arrays and delta arrays. Whatever the case may be, these filter segments are arranged squarely in a predetermined arrangement for each color.

In a color imaging apparatus using a complementary metal oxide semiconductor (C-MOS) or a charge coupled device (CCD), generally, three primary colors of additive mixing, that is, blue (B), green And color filters of yellow (Y), magenta (M), and cyan (C) colors, which are complementary colors thereof, are arranged. In recent years, there has been a growing demand for color filters such as color filters used in color image pickup devices, such as high transmittance, i.e., color characteristics such as high brightness and a wide color reproduction area.

Examples of the method of producing the color filter include a method of using a dye as a coloring agent such as a dyeing method using a coloring of a salt and a dye dispersion method, a pigment dispersion method using a pigment as a coloring agent, a printing method, and an electrodeposition method have.

In the pigment dispersion method, a color resist obtained by dispersing pigment particles as a coloring agent in a transparent resin, and mixing a photosensitive agent, an additive and the like is used. Then, the color resist is coated on a substrate by a coating device such as a spin coater, and then an aligner or a stepper is used to selectively expose the coating to the coating film through a mask. This coated film after exposure is sequentially provided to alkali development and heat curing treatment to obtain a filter segment pattern. The above operation is repeated for each color to complete the color filter.

Conventionally, a blue filter segment and a cyan filter segment are often used with a phthalocyanine pigment excellent in resistance and color tone. Phthalocyanine pigments have other crystal forms such as?,?,?, And?, And all have excellent properties such as high saturation and high coloring power. Therefore, they are suitable as colorants for color filters.

It is known that phthalocyanine pigments have various central metals such as copper, zinc, nickel, cobalt and aluminum. Among them, copper phthalocyanine pigments are widely used because they are the most expensive. In addition, dissimilar metal phthalocyanine pigments such as metal phthalocyanine pigments, zinc phthalocyanine pigments, aluminum phthalocyanine pigments, and cobalt phthalocyanine pigments have been put to practical use.

In a conventional liquid crystal display using a cold cathode tube type backlight, for example, by using a combination of a copper phthalocyanine pigment and a dioxazine-based pigment in a blue filter segment or a cyan filter segment, a high brightness and a wide color display region can be achieved Could. However, as described above, color filters are required to have a higher definition and a larger color reproduction area.

Japanese Unexamined Patent Publication No. 6-75375 discloses a technique of dissolving a dye as a coloring agent in a resin instead of a pigment in order to solve the above problems. Japanese Unexamined Patent Publication No. 8-327811 discloses an ink for a color filter containing a phthalocyanine dye and a xanthene dye. Japanese Patent Application Laid-Open No. 11-223720 discloses that a triphenylmethane dye and a xanthene dye are used together in a blue filter segment of a color filter. However, there is a problem that the dye is poor in heat resistance, light resistance and solvent resistance as compared with the pigment.

Japanese Patent Application Laid-Open No. 6-51115 and Japanese Patent Application Laid-Open No. 6-194828 disclose the use of an amine salt of an acidic dye such as a copper phthalocyanine-based acid dye or a sulfonamide compound of an acidic dye as a coloring agent for a color filter. However, the salt formation products disclosed herein are poor in solvent solubility and have not sufficient heat resistance and light resistance.

It is an object of the present invention to provide a color filter excellent in color characteristics, heat resistance, light resistance and solvent resistance, a color display including such a color filter, and a blue coloring composition used for manufacturing the color filter.

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that by using a product obtained by salt-forming a compound having a xanthene group and a xanthene acid dye as a colorant in a coloring composition, , And it has been found that excellent performance can be achieved also for heat resistance, light resistance and solvent resistance. Based on this finding, the inventions according to the following first to third aspects have been achieved.

That is, the first aspect of the present invention relates to a color filter comprising a binder resin and a coloring agent, wherein the coloring agent comprises a blue pigment and a salt formation product, and the salt formation product is a blue color filter for a color filter formed from a compound having a xanthene acid dye and a cationic group ≪ / RTI >

The compound having a cationic group may include at least one selected from the group consisting of a quaternary ammonium compound, an amine, and a resin having a cationic group in a side chain.

The compound having a cationic group may include a quaternary ammonium compound represented by the following general formula (1).

In general formula (1):

[In the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion.]

The molecular weight of the cation of the quaternary ammonium compound represented by the general formula (1) may be in the range of 190 to 900.

In the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and two or more of R ₁ to R ₄ may have 5 to 20 carbon atoms.

The compound having a cationic group includes a resin having a cationic group in the side chain, and the resin having a cationic group in the side chain may be an acrylic resin including a structural unit represented by the following formula (2).

The general formula (2)

[In the general formula (2), R ₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₆ to R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and two of R ₆ to R ₈ are bonded to each other to form a ring . Q represents an alkylene group, an arylene group, -CONH-R ₉ -, or -COO-R ₉ -, and R ₉ represents an alkylene group. Y ^- represents an inorganic or organic anion.]

The compound having a cationic group includes an amine, and the amine may be at least one selected from the group consisting of a primary amine, a secondary amine and a tertiary amine.

The molecular weight of the amine may be in the range of 129 to 591.

The amine may be represented by the following general formula (3).

The general formula (3)

R ₁₀ R ₁₁ R ₁₂ N

[In the formula (3), two of R ₁₀ to R ₁₂ each independently represent an alkyl group having 8 to 22 carbon atoms or a benzyl group, and one of R ₁₀ to R ₁₂ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms Or a benzyl group.]

The salt formation product is prepared by mixing a resin having a cationic group in the side chain and the xanthene acid dye in an aqueous solution and removing a salt comprising a counter anion of the resin having a cationic group and a counter cation of the xanthene acid dye in the side chain The resulting compound may be used,

The blue pigment may be a phthalocyanine pigment and / or a triarylmethane lake pigment.

Wherein the blue pigment comprises a phthalocyanine-based pigment, and the phthalocyanine-based pigment includes C.I. Pigment Blue 15: 6.

The xanthene acid dye is a C.I. It may be classified as an acid red.

The xanthene acid dye is a C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, and C.I. Acid Red 388. < tb > < TABLE >

The colorant may be C.I. Pigment violet 23 may be further included.

The colorant may further contain a dioxazine-based pigment.

Or an amine compound of copper phthalocyanine.

The amine compound of copper phthalocyanine may have the structure represented by general formula (4).

In general formula (4):

P-Lm

Wherein P is an m-valent copper phthalocyanine pigment residue, m is an integer of 1 to 4, and L is any one selected from the group consisting of substituents represented by the general formulas (5) to (7) .]

The general formula (5)

In general formula (6):

(7): < EMI ID =

[Among the general formulas (5) to (7)

A bond, or directly, - X is _{-SO 2 -, -CO-, -CH 2} -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2

Y ⁰ is -NH-, -O-, or a direct bond,

n is an integer of 1 to 10,

Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ - or a direct bond,

R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,

Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ² are combined to form a nitrogen, oxygen, or sulfur atom Further comprising a heterocyclic ring,

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms ,

R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,

R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6)

Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6).

The mass ratio of the xanthene dye to the amine compound of the copper phthalocyanine may be in the range of 0.3 to 1.5.

The blue pigment may be a copper phthalocyanine pigment.

The xanthene dye may be a rhodamine dye.

When the content of the blue pigment is 100 parts by mass, the amount of the effective dye component in the salt formation product (A) may be in the range of 5 to 150 parts by mass.

The blue coloring composition for a color filter may further contain a photopolymerizable compound and / or a photopolymerization initiator.

The blue coloring composition for a color filter may further contain an organic solvent containing propylene glycol monomethyl ether acetate as a main component.

The coating film formed from the colored composition so that the spectral transmittance at 570 nm is 3% has a spectral transmittance of 50% at a wavelength of 490 to 510 nm, a spectral transmittance of at least 85% at a wavelength of 450 nm, May have a spectral transmittance of 11% or less.

A second aspect of the invention relates to a color filter comprising a green filter segment, a red filter segment and a blue filter segment formed from the blue coloring composition according to the first aspect.

The color filter may be used for a solid-state image sensor.

The color filter may be used for an organic EL display.

From the white light-emitting organic EL device, the emission spectrum has two or more maximum values within a wavelength range of 400 to 700 nm, and within a range of wavelengths 430 to 485 nm and within a range of wavelengths 580 to 620 nm, a peak wavelength? ₁ and it has a λ _2, the wavelength ratio I ₂ / I ₁ of the light intensity I ₁ of the light intensity I ₂ at λ ₂ and the wavelength λ ₁ is and emit white light in the range of 0.4 to 0.9, and the white light of the blue When entering the filter segment, the chromaticity coordinates (xB, yB) in the CIE colorimetric system of the transmitted light emitted by the blue filter segment may satisfy the relationship represented by the inequalities xB? 0.160 and yB? 0.100.

From the white light-emitting organic EL device, the emission spectrum has two or more maximum values within a wavelength range of 400 to 700 nm, and within a range of wavelengths 430 to 485 nm and within a range of wavelengths 580 to 620 nm, a peak wavelength? ₁ and has a λ _2, the wavelength ratio I ₂ / I ₁ of the light intensity I ₁ of the light intensity I ₂ at λ ₂ and the wavelength λ ₁ is and emit white light in the range of 0.4 to 0.9, wherein the white light red (XR, yR), (xG, yG) and (xB, yB) in the CIE colorimetric system of the transmitted light emitted by the blue, green and red filter segments, respectively, The area of the triangle is not less than 85% of the area of the triangle whose vertex coordinates are (0.67, 0.33), (0.21, 0.71), and (0.14, 0.08) do.

The red filter segment may include C.I. Pigment Red 177 and C.I. Pigment Red 179 may be included.

The green filter segment may include C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. At least one green pigment selected from the group consisting of Pigment Green 58 and C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. And Pigment Yellow 185. The yellow pigment may be at least one kind selected from the group consisting of Pigment Yellow 185 and the like.

A third aspect of the present invention relates to a color display comprising a color filter according to the second aspect and a light emitting device including a white light emitting organic EL element as a light source.

1 is an emission spectrum of a certain backlight.
2 is an emission spectrum of an organic EL device.
3 is a light emission spectrum of another organic EL device.

Hereinafter, an aspect of the present invention will be described.

Here, "(meth) acryloyl", "(meth) acryl", "(meth) acrylic acid", "(meth) acrylate" and " Acrylate and / or methacrylate ", " acrylate and / or methacrylate ", and " acrylate and / or methacrylate & Amide and / or methacrylamide ". "C.I." means a color index (C.I.).

○ The first sun

First, the first aspect will be described.

The blue coloring composition for a color filter according to the first aspect contains a binder resin and a colorant. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed from a compound having a cationic group and a xanthene acid dye. In this embodiment, a quaternary ammonium compound is used as a compound having a cationic group.

When the blue coloring composition according to the first aspect is used in the production of a color filter, it becomes possible to realize a high brightness and a broad color reproduction area, and excellent performance can be achieved also for heat resistance, light resistance and solvent resistance.

In addition, the transmission spectrum of a blue coloring composition for a color filter in which a conventional copper phthalocyanine blue pigment and a dioxazine-based pigment are combined has a peak position near 450 nm and a transmittance sharply lowered on a short wavelength side of 450 nm or shorter.

On the other hand, when the blue coloring composition for a color filter according to the present embodiment is used, a high transmittance is achieved at a short wavelength side of 450 nm or less as compared with the case of using a combination of a copper phthalocyanine blue pigment and a dioxazine pigment. The emission spectrum of most backlights, such as cold-cathode tubes, has a peak wavelength in or near the wavelength range of, for example, 425 to 440 nm. Therefore, the filter segment obtained from the blue coloring composition for a color filter according to the present embodiment can achieve high brightness.

<Colorant>

The coloring agent of the blue coloring composition for a color filter according to the present invention contains a coloring product (A) comprising a xanthene acid dye and a quaternary ammonium compound and a blue pigment. By using the salt formation product (A) and the blue pigment in combination, a high transmittance can be achieved in the wavelength range of 425 to 440 nm or in the vicinity thereof as described above. Therefore, it is possible to realize high brightness and wide color reproduction as compared with the conventional filter segment in which a copper phthalocyanine pigment and a dioxazine pigment are combined. In addition, it is possible to realize high heat resistance, light resistance and solvent resistance by salt-forming a xanthene acid dye and a quaternary ammonium compound.

(A salt formation product (A) comprising a xanthene acid dye and a quaternary ammonium compound)

First, the salt formation product (A) will be described. The xanthene-based acid dye used in the preparation (A) of a salt formation comprising a xanthene acid dye and a quaternary ammonium compound exhibits red to purple color and has a dye form.

The xanthene-based acid dyes exhibiting red to purple color are C.I. Acid Red and C.I. Acid dyes such as Acid Violet; Direct Red and C.I. Direct violet and the like. Here, since the direct dye has a sulfonic acid group, it is considered to be an example of an acid dye in this embodiment.

The salt formation product (A) belongs to a salt dye which is formed by kneading from a quarten-based acid dye (including a direct dye) and a quaternary ammonium compound which is a counter component for generating a counter ion, and if necessary, denatured.

[Xanthane acid dye]

The acid dyes of xanthene dyes will be explained. As acid dyes for xanthene dyes, C.I. Acid Red 51 (erythrosine (edible red No. 3)), C.I. Acid Red 52 (acacid rhodamine), C.I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. Acid red 92 (Acid floc Shin PB (edible red No. 104)), C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. Acid Violet 9, C.I. Acid Violet 9, C.I. Acid Violet 30 is preferably used.

Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388 is preferably used.

Wherein the xanthene acid dye has a transmittance of 90% or more for light having a wavelength of 650 nm, a transmittance of 75% or more for light having a wavelength of 600 nm, a transmittance of 5% or less for light having a wavelength of 550 nm, It is preferable that the transmittance is 70% or more. More preferably, it is more preferable that the transmittance is 95% or more for light having a wavelength of 650 nm, the transmittance is 80% or more for a light having a wavelength of 600 nm, the transmittance is 10% or less for light having a wavelength of 550 nm, The transmittance is 75% or more.

As the xanthene-based acid dye, it is preferable to use a rhodamine-based acid dye because of its excellent coloring ability.

[Quaternary ammonium compound]

Next, the quaternary ammonium compound will be described. Since the quaternary ammonium compound has an amino group, the ion is used as a counter ion of an acidic dye.

Preferred quaternary ammonium compounds are colorless or white.

Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength range of 400 to 700 nm which is a visible light region. That is, it is necessary that the quaternary ammonium compound does not inhibit the color development of the dye component and does not cause the color change.

The molecular weight of the counter ion which is a cation component of the quaternary ammonium compound is preferably in the range of 190 to 900. [ Here, the cation portion corresponds to a portion of (NR ₁ R ₂ R ₃ R ₄ ) ^{+ in} the following general formula (1). When a cation moiety having a molecular weight of less than 190 is used, it is difficult to achieve high light resistance and heat resistance, and the solubility in the solvent is also low. When the molecular weight is more than 900, the proportion of the coloring component in the molecule is lowered, and the coloring property is lowered and the brightness is also lowered. More preferably, the molecular weight of the counter portion is in the range of 240 to 850. Particularly preferably, the molecular weight of the counter portion is in the range of 350 to 800.

Here, the molecular weight is calculated based on the structural formula. The atomic weight of C is 12, the atomic weight of H is 1, and the atomic weight of N is 14.

As the quaternary ammonium compound, those represented by the following general formula (1) are used.

In general formula (1):

(In the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and R ₁ to R ₄ And the number of C is 5 to 20 in two or more of them. Y represents an inorganic or organic anion.)

When the number of at least two of R &_lt; ₁ &gt; to R &_lt; ₄ &_gt; is 5 to 20, solubility in a solvent becomes good. When three or more alkyl groups having a number C of less than 5 are present, the solubility in a solvent is deteriorated, and a foreign matter on the coating film is likely to be generated. Also, if an alkyl group having a number of C of more than 20 is present, the coloring property of the salt formation product (A) is impaired.

Specific examples of the quaternary ammonium compound include tetramethylammonium chloride (molecular weight of cation portion is 74), tetraethylammonium chloride (molecular weight of cation portion is 122), monostearyltrimethylammonium chloride (Molecular weight of the cation portion is 284), triethylaniline monomethylammonium chloride (molecular weight of the cation portion is 788), cetyltrimethylammonium chloride (molecular weight of the cation portion is 284), triaryldimethylammonium chloride Octylmethylammonium chloride (molecular weight of the cation portion is 368), dioctyldimethylammonium chloride (molecular weight of the cation portion is 270), monolauryltrimethylammonium chloride (molecular weight of the cation portion is 228), dilauryldimethylammonium chloride Molecular weight of 382), and trilaurylmethylammonium chloride (the molecular weight of the cation moiety is 536), triamylbenzylammonium chloride (molecular weight of cation portion is 318), trihexylbenzylammonium chloride (molecular weight of cation portion is 360), trioctylbenzylammonium chloride (molecular weight of cation portion is 444), trilaurylbenzylammonium (Molecular weight of cation portion is 612), benzyldimethylstearyl ammonium chloride (molecular weight of cation portion is 388), and benzyldimethyloctylammonium chloride (molecular weight of cation portion is 248), or dialkyl (alkyl is C14 to C18) It is preferable to use dimethyl ammonium chloride (cured wurst) (molecular weight of the cation part is 438 to 550).

The component Y ^- constituting the anion may be any of an inorganic anion and an organic anion, preferably a halogen, and usually chlorine.

Examples of commercially available quaternary ammonium compounds include Kotamine 24P, Kotamine 86P, Kotamine 60W, Kotamine 86W, Kotamine D86P, Sannizol C and Sannizol B-50, manufactured by Kao Corporation, 2O-75I, 2HP-75 and 2HP flakes. Among them, Kotamine D86P (distearyldimethylammonium chloride) and Arquad 2HT-75, 2HT- 75 (dialkyl (alkyl di C14 to C18) dimethyl ammonium chloride) is preferable.

[Condensation treatment]

The crude product of the xanthene acid dye and the quaternary ammonium compound can be synthesized by a conventionally known method. Japanese Patent Application Laid-Open No. 11-72969 discloses a specific method.

For example, after the xanthene acid dye is dissolved in water, a quaternary ammonium compound is added and the solution is subjected to a coagulation treatment with stirring. Here, the sulfonate group (-SO ₃ H) of the xanthene acid dye is combined with the ammonium group (NH ₄ ⁺ ) of the quaternary ammonium compound to obtain the salt formation product. At the time of coagulation, methanol or ethanol may be used instead of water as a solvent.

The amount of the salt formation product (A) is preferably in the range of 1 to 80 parts by mass, more preferably in the range of 5 to 60 parts by mass with respect to 100 parts by mass of the blue pigment. When the amount of the salt formation product (A) is less than 1 part by mass, reproducible chromaticity regions become narrow, while when it exceeds 80 parts by mass, desired colors may not be obtained.

Particularly, C.I. The product (A) with a quaternary ammonium compound having an acid red 289 and a quaternary ammonium compound having a cation moiety in a molecular weight range of 350 to 800 is excellent in solvent solubility and has excellent heat resistance, light resistance and solvent resistance . The reason why the salt formation product (A) is used in combination with the blue pigment to achieve good performance is that the salt formation product (A) is adsorbed on the blue pigment while being dissolved or dispersed in the solvent.

(Blue pigment)

As the blue pigment, a phthalocyanine pigment and / or a triarylmethane lake pigment can be used. As the phthalocyanine-based pigment, it is preferable to use a copper phthalocyanine blue pigment.

As the copper phthalocyanine blue pigment, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 2, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, and C.I. Pigment Blue 15: 6, and among them, a copper phthalocyanine blue pigment having a structure of? Or? Type is preferable. These preferred pigments are specifically C.I. Pigment Blue 15: 6 and C.I. Pigment Blue 15: 1.

As the triarylmethane lake pigment, C.I. Pigment Blue 1, C.I. Pigment Blue 1: 2, C.I. Pigment Blue 1: 3, C.I. Pigment Blue 2, C.I. Pigment Blue 2: 1, C.I. Pigment Blue 2: 2, C.I. Pigment Blue 3, C.I. Pigment Blue 8, C.I. Pigment Blue 9, C.I. Pigment Blue 10, C.I. Pigment Blue 10: 1, C.I. Pigment Blue 11, C.I. Pigment Blue 12, C.I. Pigment Blue 18, C.I. Pigment Blue 19, C.I. Pigment Blue 24, Copper 24: 1, C.I. Pigment Blue 53, C.I. Pigment Blue 56, C.I. Pigment Blue 56: 1, C.I. Pigment Blue 57, C.I. Pigment Blue 58, C.I. Pigment Blue 59, and C.I. Pigment Blue 61, C.I. Pigment Blue 62 and the like.

C.I. Pigment Blue 15: 6 is preferably used.

[Minification of Pigment]

The blue pigment used in the blue coloring composition of this embodiment and other pigments optionally used may be finely ground by a salt milling treatment. The primary particle diameter of the pigment is preferably 20 nm or more in view of good dispersion into the colorant carrier. The primary particle diameter of the pigment is preferably 100 nm or less in that a filter segment having a high contrast ratio can be formed. A particularly preferable range is 25 to 85 nm.

The diameter of the primary particles of the pigment is determined from an electron microscope photograph of the pigment by a TEM (transmission electron microscope). Specifically, first, in the TEM image, one pigment particle as a primary particle in which the whole is visible is selected. Next, among the line segments connecting the two points on the outline of the pigment particle image, the one having the maximum length is selected. This line segment is set as the first line segment. Then, among the line segments connecting the two points on the contour of the pigment particle image, the one that is orthogonal to the first line segment is selected. This line segment is referred to as the second line segment. And, to obtain an average of the first length of the line segment (L ₁₎ and the length of the second line segment (L ₂₎ as the average length (L _av), also the volume of the same cube and 1 have an average length (L _av) side length ( V). The above measurement and calculation are performed on 100 or more pigment particles, and the average of the volume (V) is obtained as the average volume (V _av ). The length of one side of the cube having this average volume (V _av ) is defined as the average primary diameter of the pigment particles.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor and a sand mill, And removing the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid. At the time of salt milling, the pigment is crushed using the height of the hardness of the inorganic salt. By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very small primary particle diameter and a narrow distribution width and having a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, and sodium sulfate can be used. In terms of price, it is preferable to use sodium chloride (salt). The water-soluble inorganic salt is preferably used in an amount of from 50 to 2000 parts by mass, preferably from 300 to 1000 parts by mass, based on both the treatment efficiency and the production efficiency, when the total mass of the pigment is 100 parts by mass desirable.

The water-soluble organic solvent is not particularly limited so long as it acts to wet the pigment and the water-soluble inorganic salt, dissolves in water (miscible) and does not substantially dissolve the inorganic salt used. However, since the temperature rises at the time of the salt milling and the solvent becomes easy to evaporate, a high boiling point solvent having a boiling point of 120 캜 or higher is preferable from the viewpoint of safety. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Monoethyl ether, or liquid polypropylene glycol is used. When the total mass of the pigment is 100 parts by mass, the water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass.

When the pigment is subjected to the salt milling treatment, a resin may be added. The kind of the resin is not particularly limited, and for example, a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin can be used. The resin is preferably a solid at room temperature, preferably water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 parts by mass when the total mass of the pigment is 100 parts by mass.

(Other coloring agent)

Other organic pigments may be added to the blue coloring composition of the present invention as long as they do not interfere with the effect.

As the organic pigment, for example, a dioxazine pigment, an anthraquinone pigment, an azo pigment, or a quinacridone pigment is preferably used. Among them, it is preferable to use a dioxazine-based pigment. As the dioxazine-based pigment, C.I. Pigment Violet 23 is preferably used. When a dioxazine-based pigment is used, a high-quality blue coloring composition having excellent heat resistance, light resistance and solvent resistance can be obtained.

It is preferable that the organic pigment is also finely ground by a method such as salt milling as described above.

<Resin>

Resins are those in which the coloring agent, in particular the crude salt product, is dispersed, or the crude product is dyed or penetrated. Examples of the resin include a thermoplastic resin and a thermosetting resin.

The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light region. When the blue coloring composition is used in the form of an alkali developing type coloring resist material, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. Further, in order to further improve the light sensitivity, an active energy ray-curable resin having an ethylene bond may be used.

In particular, when an active energy ray-curable resin having an ethylene bond in its side chain is used in an alkali development type resist for a color filter, no foreign matter is formed on the coating film formed by applying the active energy ray-curable resin and the stability of the salt formation product (A) . When a linear resin having no ethylene bond in the side chain is used, the dye is difficult to be trapped in the resin in a liquid in which the resin and the dye are mixed, and the aggregation and precipitation tend to occur. In the case of using an active energy ray-curable resin having an ethylene bond in the side chain, in the liquid in which the resin and the dye are mixed, the dye is apt to be trapped in the resin, and therefore, the aggregation and precipitation hardly occur. In this case, when the coating film is exposed with an active energy ray, the resin is three-dimensionally crosslinked, and the position of the dye molecule is fixed. Therefore, even when the solvent is removed in the subsequent developing step, coagulation and precipitation of the dye hardly occur.

The weight average molecular weight (Mw) of the resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to disperse the colorant (B) well. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 10 or less.

When the blue coloring composition is used as a photosensitive coloring composition for a color filter, from the viewpoints of dispersibility or solubility and developability and heat resistance of the pigment and the salt formation product, a coloring agent adsorber and a carboxyl group serving as an alkali- And the balance between an aliphatic group and an aromatic group serving as an affinity group for a solvent are important. It is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. A resin having an acid value of less than 20 mg KOH / g is poor in solubility in a developing solution, and it is difficult to form a fine pattern. If the acid value exceeds 300 mgKOH / g, both of the exposed portion and the unexposed portion may be removed by development.

When the total mass of the colorant is 100 parts by mass, the resin is preferably used in an amount of 30 parts by mass or more from the viewpoint of achieving excellent film formability and various durability, and from the viewpoint of achieving high colorant concentration and good color characteristics, It is preferable to use it in an amount of not more than 1 part by mass.

(Thermoplastic resin)

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane- (HDPE, LDPE), polybutadiene, and polyimide resin, and the like can be given as examples of the resin composition of the present invention.

Examples of the vinyl-based alkali-soluble resin containing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an? -Olefin- (anhydrous) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, an ethylene- (meth) acrylic acid copolymer, or an isobutylene- ) Maleic acid copolymer, and the like. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene-styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is suitably used because of its high heat resistance and transparency.

Examples of the active energy ray-curable resin having an ethylene bond include a resin into which an ethylene bond has been introduced by the following method (a) or (b).

[Method (a)]

In the method (a), for example, a copolymer having an epoxy group in the side chain is obtained by first copolymerizing a monomer having an epoxy group and an ethylene bond and at least one other monomer. Subsequently, the carboxyl group of the unsaturated monobasic acid having an ethylenic bond and a carboxyl group is subjected to an addition reaction with the epoxy group of the side chain, and the resulting hydroxyl group is reacted with the acid anhydride. Thus, a resin having an ethylene bond and a carboxyl group introduced therein is obtained.

Examples of the monomer having an epoxy group and an ethylene group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (Meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and hydrogen atoms in the? -Position of (meth) acrylic acid with a haloalkyl group, an alkoxyl group, a halogen atom , A nitro group or a cyano group, and the like. These may be used alone or in combination of two or more.

Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more.

Instead of an anhydride of an acid having two carboxyl groups or an acid anhydride having two carboxyl groups, an anhydride of an acid having three or more carboxyl groups such as trimellitic anhydride A tetracarboxylic acid dianhydride such as an anhydride or pyromellitic dianhydride may be used. In this case, the residual anhydride group after the reaction between the hydroxyl group and the acid anhydride may be hydrolyzed.

As the acid anhydride, an acid anhydride having an ethylene bond such as tetrahydrophthalic anhydride and maleic anhydride may be used. This can further increase the ethylene bond.

Further, as a method similar to the method (a), for example, there are the following methods. First, a copolymer in which a monomer having a carboxyl group and an ethylene bond is copolymerized with at least one other monomer to obtain a copolymer having a carboxyl group in its side chain. Subsequently, a monomer having an ethylene bond and an epoxy group is added to a part of the carboxyl group of the side chain. Thus, a resin having an ethylene bond and a carboxyl group introduced therein is obtained.

[Method (b)]

In the method (b), for example, a monomer having a hydroxyl group and an ethylene bond is first copolymerized with an unsaturated monobasic acid or an other monomer having a carboxyl group and an ethylene bond to obtain a copolymer having a hydroxyl group in the side chain . Subsequently, an isocyanate group of a monomer having an isocyanate group and an ethylene bond is reacted with the hydroxyl group of the side chain. Thus, a resin having an ethylene bond and a carboxyl group introduced therein is obtained.

Examples of the monomer having a hydroxyl group and an ethylene group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as methyl (meth) acrylate, glycerol (meth) acrylate, and cyclohexanedimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. Further, a compound obtained by addition polymerization of an oxide such as ethylene oxide, propylene oxide, and butylene oxide to hydroxyalkyl (meth) acrylate such as polyether mono (meth) acrylate or hydroxyalkyl (metha) (Poly) ester mono (meth) acrylate obtained by adding at least one of (poly)? -Valerolactone, (poly)? -Caprolactone and (poly) Can be used. 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter traces on the coating film.

Examples of the monomer having an isocyanate group and an ethylene bond include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate. These may be used alone or in combination of two or more.

(Thermosetting resin)

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

<Solvent>

The blue coloring composition of the present invention can be used, for example, to easily disperse or dissolve a coloring agent in a coloring agent carrier and to form a filter segment by applying a dry film thickness of 0.2 to 5 μm on a substrate such as a glass substrate A solvent may be contained.

Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4 Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3- 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl Acetone, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n- Propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, Isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethylene glycol monopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, Hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetic acid Diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether , Propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene N-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters such as methyl ethyl ketone, methyl isobutyl ketone, methyl isobutyl ketone, n-amyl acetate, The can.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether (A) are preferable from the viewpoint of good dispersibility and solubility of the pigment and the salt formation product Acetates and the like, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferably used.

The solvent may be used alone or in combination of two or more. The solvent is used in an amount of 800 to 4000 parts by mass based on 100 parts by mass of the total mass of the coloring agent since the coloring composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness .

<Dispersion>

This blue coloring composition is obtained by mixing a coloring agent containing a blue pigment and a salt formation product (A) in a coloring agent carrier comprising a resin and a solvent to be used as required, preferably with a dispersion aid such as a pigment derivative, To a treatment using various dispersing means such as sand mill, kneader, and stirrer. The blue coloring composition may also be produced by dispersing several kinds of coloring agents in a coloring agent carrier, and then mixing them.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, a dispersion aid such as a pigment derivative, a resin type dispersant and a surfactant may be suitably used. The dispersing aid is excellent in the ability to disperse the coloring agent and has a great effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, when a coloring composition comprising a coloring agent dispersed in a pigment carrier using a dispersion aid is used, a color filter having a high spectral transmittance can be obtained.

Further, in the present embodiment, the salt formation product (A) can serve as a dispersing aid for the blue pigment.

Examples of the pigment derivative include compounds in which a phthalimidomethyl group, which may have a basic substituent, an acidic substituent or a substituent, is introduced into an organic pigment, anthraquinone, acridone or triazine.

Of these, pigment derivatives are preferred. And its structure is represented by the following general formula (2).

P-Ln (2)

Wherein P represents an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue, L represents a phthalimidomethyl group which may have a basic substituent, an acidic substituent or a substituent, and n represents an integer of 1 to 4 It is an integer.

As the organic pigments constituting the organic pigment residue, for example, diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone and violanthrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Trene pigments; And metal complex system pigments.

Examples of the pigment derivative include those described in Japanese Patent Laid-Open Nos. 63-305173, 57-15620, 59-40172, 63-17102, and 5-9469 Can be used. These may be used alone or in combination of two or more.

The blending amount of the colorant derivative is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more, when the total amount of the colorant is 100 parts by mass, from the viewpoint of improvement of dispersibility. The blending amount of the dye derivative is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, when the total amount of the colorant is 100 parts by mass from the viewpoint of heat resistance and light resistance.

The resinous dispersant has a colorant-affinity site having a property of adsorbing to a colorant and a site compatible with the colorant carrier, and adsorbs on the colorant to stabilize the dispersion of the colorant in the colorant carrier. Specific examples of the resinous dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, poly An amide formed by reaction of a poly (alkylene amine) salt of a carboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, a modified product thereof, a poly (lower alkyleneimine), and a polyester having a liberated carboxyl group Or a salt thereof, a water-soluble resin such as a (meth) acrylic acid-styrene copolymer, a (meth) acrylic acid- (meth) acrylic acid ester copolymer, a styrene-maleic acid copolymer, polyvinyl alcohol and polyvinylpyrrolidone Or water-soluble polymer compounds, polyester dispersants, modified polyacrylate dispersants, ethylene oxide / propylene oxide It is a compound, and a phosphoric acid ester-based dispersion agent is used. These may be used alone or in combination of two or more. The resinous dispersant is not necessarily limited to these.

Examples of commercially available resinous dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 , 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150 and 2155, Anti-Terra-U, 203 and 204, BYK 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, etc., manufactured by Nippon Lubrizol Corporation, and Lactimon- 46, 47, 48, and 50 available from Chiba Japan Co., Ltd., and EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, PB111, PB711, PB821, and PB822 of Ajinomoto Fine Techno Co., Ltd. were added to the mixture, And PB824.

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, alkyldiphenyl ether disulfonic acid Anionic surfactants such as sodium laurylsulfate monoethanolamine, laurylsulfate triethanolamine, ammonium laurylsulfate, stearic acid monoethanolamine, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphoric acid esters ; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate ; Cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; Alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline. These may be used alone or in combination of two or more. The surfactant is not necessarily limited to these.

When a resinous dispersant and / or a surfactant is added, the amount thereof is preferably in the range of 0.1 to 55 parts by mass, more preferably in the range of 0.1 to 45 parts by mass, based on 100 parts by mass of the total amount of the colorant Do. When the blending amount is less than 0.1 part by mass, the effect of the resin type dispersing agent and / or the surfactant is hardly obtained. When the blending amount is more than 55 parts by mass, the dispersion may be caused by an excessive dispersing agent.

The blue coloring composition of this embodiment can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable compound and / or a photopolymerization initiator.

&Lt; Photopolymerizable compound >

The photopolymerizable compound includes a monomer or an oligomer which is cured by ultraviolet rays or heat to produce a transparent resin. These may be used alone or in combination of two or more. The blending amount of the photopolymerizable compound is preferably in the range of 5 to 400 parts by mass when the total mass of the colorant is 100 parts by mass, and more preferably in the range of 10 to 300 parts by mass from the viewpoints of photo-curability and developability.

Examples of the monomer or oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (Meth) acrylate,? -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6- hexane diol diglycidyl ether di (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta Various acrylic esters such as (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylate of methylol melamine, epoxy (meth) acrylate, and urethane acrylate, and methacrylic acid ester; (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Monomers other than (meth) acrylate such as amide and acrylonitrile; And oligomers thereof. These may be used alone or in combination of two or more. The monomer or oligomer is not necessarily limited to these.

<Photopolymerization initiator>

When a filter segment of a color filter is formed from a blue coloring composition by a photolithography method using ultraviolet irradiation, this coloring composition can be obtained by adding, for example, a photopolymerization initiator or the like, in the form of a solvent developing type or an alkali developing type coloring resist material use. When a photopolymerization initiator is used, the blending amount thereof is preferably in the range of 5 to 200 parts by mass when the total amount of the colorant is 100 parts by mass, more preferably in the range of 10 to 150 parts by mass from the viewpoints of photo- More preferable.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2- (4-morpholinophenyl) -1-butanone, and 2-benzyl-2-dimethylamino-1- (4- Butane-1-one; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; Thioxanthone systems such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and 2,4- compound; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) (Trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) - (4-methoxy-naphthol- Triazine-based compounds such as 6-triazine, and 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 2-oxo-2- (4 ', 5'-tetradecyloxy) -Methoxy-naphthyl) ethylidene) hydroxylamine and the like; Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphaquinone, and ethyl anthraquinone; Borate compounds; Carbazole-based compounds; Imidazole-based compounds; And titanocene compounds.

These photopolymerization initiators may be used singly or in combination of two or more in an arbitrary ratio. These photopolymerization initiators are preferably used in an amount of 5 to 200 parts by mass when the total amount of the coloring agent in the coloring composition for a color filter is 100 parts by mass and in an amount of 10 to 150 parts by mass in view of photocurability and developability .

<Increase / decrease>

A blue coloring composition for a color filter may further contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives represented by benzyl and campquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, Anthraquinone derivatives, xanthine derivatives, thioxanthone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives and oxoline derivatives, A derivative thereof, an azine derivative, a thiazine derivative, an oxazine derivative, an indoline derivative, an azulene derivative, an azulenium derivative, a squarylium derivative, a porphyrin derivative, a tetraphenylporphyrine derivative, a triarylmethane derivative, a tetrabenzoporphyrin derivative, A pyrazine derivative, a phthalocyanine derivative, a tetraazaporphyrazine derivative, a tetraquinazolinoporphyrazine derivative , A naphthalocyanine derivative, a subphthalocyanine derivative, a pyrylium derivative, a thiopyrylium derivative, a tetrapyrin derivative, an indolene derivative, a spiropyran derivative, a spirooxazine derivative, a thiospiropyran derivative, a metal arene complex, Ketone derivatives,? -Acyloxy esters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphaquinone, ethyl anthraquinone, 4,4'-diethylisopthalophenone, 3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-diethylaminobenzophenone.

More specifically, it is also known as "functional coloring matter chemistry" (1981, CMC), and Ikemori Chuzoburo edited by Okawara Makoto, "Handbook of coloring" (Kodansha in 1986, Kodansha) And the sensitizer described in &quot; Special Functional Materials &quot; (CMC, 1986). The sensitizer is not limited to these. In addition, the coloring composition may contain a sensitizer that exhibits absorption of ultraviolet to near-infrared light.

Two or more kinds of sensitizers may be used at an arbitrary ratio. When the sensitizer is used, the blending amount thereof is preferably from 3 to 60 parts by mass when the total mass of the photopolymerization initiator contained in the coloring composition is 100 parts by mass, more preferably from 5 to 50 parts by mass from the viewpoint of photocurability and developability More preferable.

<Amine compound>

The coloring composition for a color filter of the present invention can further contain an amine compound having an action of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid 2-dimethylamino Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl para-toluidine.

<Leveling agent>

In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Inc. and BYK-333 manufactured by Big Chemie. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain may be used in combination. The content of the leveling agent is preferably in the range of 0.003 to 0.5% by mass, based on 100% by mass of the total mass of the coloring composition.

As the leveling agent, a compound having a hydrophobic group and a hydrophobic group in the molecule, i.e., a kind of a surfactant, has a hydrophilic group, has a low solubility in water, and has a low ability to lower its surface tension when added to a coloring composition , And it is particularly useful that the wettability to the glass plate is good. Among them, it is preferable that chargeability can be sufficiently suppressed at an addition amount at which defects of the coating film due to foam generation do not appear. As a leveling agent having such preferable characteristics, there is, for example, a dimethylpolysiloxane having a polyalkylene oxide unit. The polyalkylene oxide units include, for example, polyethylene oxide units and polypropylene oxide units. The dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit. The form of bonding of the polyalkylene oxide unit with the dimethylpolysiloxane is such that the pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, the terminal modification in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, Or a linear block copolymer type in which an oxide unit is alternately repeatedly bonded with a dimethylpolysiloxane. Examples of the dimethylpolysiloxane having a polyalkylene oxide unit include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ- 2203, and FZ-2207. The dimethylpolysiloxane having a polyalkylene oxide unit is not limited to these.

It is also possible to add anionic, cationic, nonionic, or amphoteric surfactant to the leveling agent. The surfactants may be used in combination of two or more.

Examples of the anionic surfactant to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, alkyldiphenyl ether disulfonic acid Sodium lauryl sulfate, monoethanolamine laurylsulfate, triethanolamine laurylsulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether Phosphate esters.

Examples of the cationic surfactant to be added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of the nonionic surfactant to be added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan Monostearate, polyethylene glycol monolaurate, alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazoline, and fluorine-based or silicone-based surfactants.

<Curing agent and hardening accelerator>

The coloring composition may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist curing of the thermosetting resin.

As the curing agent, for example, a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, and a sulfonic acid compound are useful. The curing agent is not particularly limited to these. Any curing agent may be used as long as it can react with the thermosetting resin. Among them, a compound having two or more phenolic hydroxyl groups in one molecule and an amine type curing agent are preferable.

Examples of the curing accelerator include dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, , N-dimethylbenzylamine; Quaternary ammonium salt compounds such as triethylbenzylammonium chloride; Block isocyanate compounds such as dimethylamine; Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl- Imidazole derivative 2-cyclic amidine compounds such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole and salts thereof; Phosphorus compounds such as triphenylphosphine; Guanamine compounds such as melamine, guanamine, acetoguanamine, and benzoguanamine; Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino- An S-triazine-isocyanuric acid adduct, and an S-triazine derivative such as 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct have. The curing accelerator may be used alone or in combination of two or more. The content of the curing accelerator is preferably in the range of 0.01 to 15% by mass based on the total amount of the thermosetting resin.

&Lt; Other additive components >

The blue coloring composition of the present invention may contain a storage stabilizer in order to keep the viscosity of the composition almost constant over a long period of time. In addition, the coloring composition may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion with the transparent substrate.

As the storage stabilizer, for example, benzyltrimethyl chloride; Quaternary ammonium chloride such as diethylhydroxyamine; Organic acids such as lactic acid and oxalic acid, and methyl ethers thereof; t-butyl pyrocatechol; Organic phosphine such as tetraethylphosphine and tetraphenylphosphine; And phosphites. The storage stabilizer may be used in an amount of, for example, 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant in the coloring composition.

Examples of the adhesion improver include vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth) acrylsilanes such as? -methacryloxypropyltrimethoxysilane; ? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane, ,? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -glycidoxypropyltrimethoxysilane, and? -glycidoxypropyltriethoxysilane; (Aminoethyl)? - aminopropyltrimethoxysilane, N -? (Aminoethyl)? - aminopropyltriethoxysilane, N -? Amino silanes such as aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane, N-phenyl-? -Aminopropyltrimethoxysilane, and N-phenyl-? -Aminopropyltriethoxysilane; And silane coupling agents such as thiosilanes such as? -Mercaptopropyltrimethoxysilane and? -Mercaptopropyltriethoxysilane. The adhesion-improving agent may be used in an amount of, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Antioxidant>

It is preferable that the blue coloring composition of the present invention further contains an antioxidant to increase the transmittance of the coating film.

The antioxidant is oxidized by the heat treatment performed in the thermosetting process and the annealing process of the ITO (indium tin oxide), etc., of the photopolymerization initiator or the thermosetting resin contained in the photosensitive blue coloring composition, and as a result, the yellowing can be prevented. Therefore, if an antioxidant is contained in the coloring composition, the transmittance of the coating film can be increased.

As the antioxidant, for example, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant or a sulfide-based antioxidant is preferably used, and a hindered phenol-based antioxidant, a hindered amine- It is more preferable to use an antioxidant or a phosphorus antioxidant. These may be used alone or in combination of two or more.

Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [ Tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t- Dihydroxy-2,6-dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy- 3,5-triazine.

Examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- 2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis , 6-tetramethyl-4-piperidyl) (1,2,3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino- 3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethyl {(2,2,6,6- Piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2,6,6- Piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4- -2,2,6,6-tetramethylpiperidine, and a polycondensate of N , N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl- 5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.

Examples of the phosphorus antioxidant include tris [2 - [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosph Yl] oxy] ethyl] amine, tris [2 - [(4,6,9,11-tetra-butyldibenzo [d, f] [1,3,2] dioxaphosphper- Yl) oxy] ethyl] amine, and ethyl bis (2,4-ditert-butyl-6-methylphenyl) phosphite.

Examples of the sulfide-based antioxidant include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] [(Octylthio) methyl] -o-cresol, and 2,4-bis [(laurylthio) methyl] -o-cresol.

The antioxidant is preferably used in an amount of 0.1 to 5 parts by mass when the total amount of solid components in the blue coloring composition is 100 parts by mass.

<Removal of Coarse Particles>

From this colored composition, coarse particles of 5 mu m or more, preferably coarse particles of 1 mu m or more, more preferably coarse particles of 0.5 mu m or more, and dust particles of mixed dust or the like are removed by means of centrifugation, sintering filter, It is preferable to carry out the removal. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 m or more. Further, it is more preferable that the coloring composition does not substantially contain particles of 0.3 mu m or more.

<Color filter>

Next, a color filter according to this embodiment will be described.

The color filter according to the present embodiment includes a plurality of filter segments that are different in absorption spectrum, and are typically arranged in a regular fashion. One form of the color filter has at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Another type of color filter has at least one magenta filter segment, at least one cyan filter segment and at least one yellow color filter segment. In a color filter according to this aspect, at least one of these filter segments, for example a blue filter segment, is formed from the coloring composition for a color filter described above.

The red filter segment can be formed from a common red coloring composition including, for example, a red pigment and a colorant carrier. As the red pigment, for example, C.I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: , 168, 169, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281 , 282, 283, 284, 285, 286 or 287 are used. An alkaline dye showing red color and a salt-forming product of acid dye may be used.

The red coloring composition includes C.I. Pigment Orange 43, 71 and 73, and C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 193, 194, 198, 199, 213, 214, 218, 219, 220 and 221. Alkali dyes showing coloration and / or yellow color and salts of acidic dyes may be used.

The green filter segments can be formed from conventional green coloring compositions, including, for example, a green pigment and a colorant carrier. As the green pigment, for example, C.I. Pigment Green 7, 10, 36, 37 or 58 is used.

In the green coloring composition, a yellow pigment may be used in combination. As the yellow pigment, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: , 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101 , 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153 , 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188 , 193, 194, 198, 199, 213, 214, 218, 219, 220 and 221. An alkaline dye showing yellow color and a salt-forming product of acid dye may be used in combination.

<Manufacturing Method of Color Filter>

This color filter can be produced by, for example, a printing method or a photolithography method.

According to the printing method, patterned filter segments can be formed only by repeating printing and drying of the coloring composition prepared as a printing ink. Therefore, the printing method is inexpensive and excellent in mass productivity. Further, by the development of printing technology, it is possible to form a fine pattern having high dimensional accuracy and smoothness by printing.

The ink used for printing preferably has a composition that is not dried and fixed on a printing plate or blanket. In the printing method, it is also important to control the fluidity of the ink on the printing press. The flowability of the ink can be controlled by adjusting the ink viscosity using a dispersing agent or extender pigment.

According to the photolithography method, the color filter can be manufactured with higher precision as compared with the printing method.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type coloring resist is applied onto the transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating , And the dry film thickness is, for example, in the range of 0.2 to 5 mu m. The coating film is dried if necessary and is passed through a mask having a predetermined pattern made in contact or noncontact state with the coating film, and the coating film is exposed to ultraviolet rays. Thereafter, the coating film is immersed in a solvent or an alkaline developing solution, or a solvent or an alkaline developing solution is sprayed onto the coating film to remove the uncured portion from the coating film. Thus, a thin film pattern corresponding to a filter segment of a certain color is obtained. The same operations as those described above are repeated to form a thin film pattern corresponding to the remaining filter segments, except that a coloring composition for filter segments of different colors is used. Thereafter, these thin film patterns are fired to obtain a color filter. The firing may be performed every time a thin film pattern is formed.

At the time of development, for example, aqueous solutions such as sodium carbonate and sodium hydroxide are used as the alkali developing solution. Organic alkali such as dimethylbenzylamine and triethanolamine may be used. A defoaming agent or a surfactant may be added to the developer.

In order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is coated on the colored resist film formed by applying and drying the colored resist, Thereafter, ultraviolet ray exposure may be performed. A coating film composed of a water-soluble or alkali-soluble resin prevents the polymerization in the colored resist film from being inhibited by oxygen.

The color filter can be manufactured by a method other than the printing method and the photolithography method. For example, a color filter can be manufactured by an electrodeposition method or a transfer method. The above-mentioned coloring composition can be used in any method.

In the manufacture of a color filter using electrodeposition, a substrate provided with a transparent conductive film on one main surface is prepared, and the filter segments are formed by electrophoresis of the colloidal particles on the transparent conductive film using the transparent conductive film as an electrode. In manufacturing the color filter using the transfer method, a filter segment is previously formed on the main surface of a transfer base sheet having one separable main surface, and the filter segment is transferred from the transfer base sheet to the substrate.

On the transparent substrate, a black matrix, which is a light-shielding pattern, may be formed before the filter segments are formed. As the black matrix, for example, a metal film such as a chromium film, a multilayer film such as a chromium / chromium oxide film, an inorganic compound film such as a titanium nitride film, or a resin film in which a light shielding material is dispersed in a resin is used.

An active matrix circuit including a thin film transistor (TFT) may be formed on the transparent substrate before a color filter is formed. Other layers such as an overcoat film and a transparent conductive film may be further formed on the color filter, if necessary.

(Example A)

Hereinafter, the present embodiment will be described on the basis of embodiments, but the present invention is not limited thereto. Unless otherwise specified, &quot; part &quot; means &quot; part by mass &quot;. The weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation). In addition, tetrahydrofuran (THF) was used as a developing solvent.

First, an acrylic resin solution, a finely divided pigment, a salt formation product (A), a xanthene compound, a pigment dispersion, a resin solution containing a salt formation product, a resin solution containing a xanthene compound, a red resist material, The manufacturing method of the ash will be described below.

&Lt; Production method of acrylic resin solutions 1A to 4A >

(Preparation of acrylic resin solution 1A)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer were attached to a separate four-necked flask, and 70.0 parts of cyclohexanone was charged into the reaction vessel. After the temperature was raised to 80 ° C and the inside of the reaction vessel was purged with nitrogen, a dropping tube was charged with 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, , 7.4 parts of 2,2'-azobisisobutyronitrile (Aronix M110 manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for further 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling the resin solution to room temperature, about 2 g thereof was sampled. This was dried by heating at 180 DEG C for 20 minutes, and the nonvolatile content was measured. Based on the thus obtained nonvolatile component content, propylene glycol monomethyl ether acetate (PGMAC) was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 1A.

(Preparation of acrylic resin solution 2A)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer were attached to a separate four-necked flask, and 207 parts of cyclohexanone was charged into the reaction vessel. After the inside of the reaction vessel was purged with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, , 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution.

Then, the supply of the nitrogen gas was stopped, and dry air was injected for one hour while stirring with respect to the total amount of the copolymer resin solution. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Carlen MOI, manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was stirred at 70 ° C for 3 hours .

Approximately 2 g of this resin solution was sampled and dried by heating at 180 캜 for 20 minutes to measure the amount of nonvolatile matter. On the basis of the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 2A. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 2A was 18,000.

(Preparation of acrylic resin solution 3A)

A separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube, and an agitator was charged with 207 parts of cyclohexanone. After raising the temperature to 80 DEG C and replacing the inside of the reaction vessel with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagose Corporation), 45 parts of methyl methacrylate , 8.5 parts of glycerol monomethacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution.

Next, the nitrogen gas was stopped, and dry air was injected into the copolymer resin solution for one hour with stirring. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate, 0.08 parts of dibutyl tin dilaurate, and 26 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours.

Approximately 2 g of the resin solution was sampled and dried by heating at 180 캜 for 20 minutes to measure the amount of nonvolatile matter. On the basis of the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 3A. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 3A was 19,000.

(Preparation of acrylic resin solution 4A)

A separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube, and an agitator was charged with 370 parts of cyclohexanone. After the temperature was raised to 80 ° C and the inside of the reaction vessel was purged with nitrogen, 18 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagose Corporation), 10 parts of benzyl methacrylate, A mixture of 18.2 parts of methyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropwise addition, the reaction was further carried out at 100 DEG C for 3 hours. Subsequently, a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added to this solution, and the mixture was further reacted at 100 DEG C for 1 hour. Thereafter, the inside of the reaction vessel was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl group), 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were charged into the vessel. The reaction was continued at 120 캜 for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the resulting hydroxyl group) and 0.5 part of triethylamine were added to the thus obtained solution, and the reaction was carried out at 120 占 폚 for 3.5 hours to obtain a solution of the acrylic resin.

After cooling the resin solution to room temperature, about 2 g thereof was sampled and dried by heating at 180 DEG C for 20 minutes, and the amount of nonvolatile matter was measured. On the basis of the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 4A. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 4A was 19,000.

&Lt; Production method of micronized pigment >

(Preparation of blue fine pigment 1A)

200 parts of CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Ink & Chemicals, Inc., specific surface area 60 m ² / g) as a phthalocyanine blue pigment, 1400 parts of sodium chloride and 360 parts of diethylene glycol were added to a stainless steel first gallon And kneaded at 80 占 폚 for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a blue fine pigment 1A. The specific surface area of the blue fine pigment 1A was 80 m ² / g.

(Preparation of blue fine pigment 2A)

200 parts of CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a triphenylmethane blue pigment, And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a blue fine pigment 2A. The specific surface area of the blue fine pigment 2A was 65 m ² / g.

(Preparation of purple fine pigment 1A)

200 parts of CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink and Chemicals, Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while being heated to 80 DEG C to obtain a slurry. The filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of purple fine pigment 1A. The specific surface area of the purple fine pigment 1A was 95 m ² / g.

(Preparation of red fine pigment 1A)

200 parts of CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Japan Co.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a diketopyrrolopyrrole type red pigment And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day and one night to obtain 190 parts of red fine pigment 1A. The specific surface area of the red fine pigment 1A was 70 m ² / g.

(Preparation of Yellow Fine Pigment 1A)

, 500 parts of CI Pigment Yellow 139 ("Irgafour Yellow 2R-CF" manufactured by Chiba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were mixed with a stainless steel first gallon kneader ), And kneaded at 120 DEG C for 8 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to obtain 490 parts of yellow fine pigment 1A. The specific surface area of the yellow fine pigment 1A was 70 m ² / g.

(Preparation of Green Fine Pigment 1A)

200 parts of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a green fine pigment 1A. The specific surface area of the green fine pigment 1A was 75 m ² / g.

(Preparation of yellow fine pigment 2A)

200 parts of CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) Over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of yellow fine pigment 2A. The specific surface area of the yellow fine pigment 2A was 65 m ² / g.

&Lt; Preparation method of salt formation product (A) >

(Preparation salt product (A-1A))

By the following procedure, C.I. (A-1A) comprising Acid Red 289 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. A crude salt product (A-1A) as a product salt product of Acid Red 289 and distearyldimethylammonium chloride was obtained.

(Preparation salt product (A-2A))

By the following procedure, C.I. (A-2A) comprising Acid Red 289 and dilauryldimethylammonium chloride (the molecular weight of the cation portion was 382) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. After the solution was heated to 70 to 90 캜, dilauryldimethylammonium chloride was added dropwise thereto. The dilauryldimethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of the dilauryldimethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes in order to sufficiently react. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-2A) as a product salt product of Acid Red 289 and dilauryldimethylammonium chloride.

(Salt formation product (A-3A))

By the following procedure, C.I. (A-3A) comprising Acid Red 289 and tristearyl monomethylammonium chloride (molecular weight of the cation portion was 788) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and trisuteryl monomethylammonium chloride was added dropwise thereto. Tristearyl monomethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of tristearyl monomethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-3A) which is a product salt product of Acid Red 289 and tristearyl monomethylammonium chloride.

(Preparation salt product (A-4A))

By the following procedure, C.I. (A-4) comprising Acid Red 52 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. To thereby dissolve the acid red 52, and this solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-4A) as a product salt of the salt of Acid Red 52 with distearyldimethylammonium chloride.

(Preparation salt product (A-5A))

By the following procedure, C.I. (A-5A) comprising Acid Red 87 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 87 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-5A) which is a product salt product of Acid Red 87 and distearyldimethylammonium chloride.

(Preparation salt product (A-6A))

By the following procedure, C.I. (A-6A) comprising Acid Red 92 and trilaurylbenzyl ammonium chloride (molecular weight of the cation portion is 612) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 92 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and trilaurylbenzylammonium chloride was added dropwise thereto. Trilaurylbenzylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of trilaurylbenzylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes in order to sufficiently react. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-6A) which is the product of the salt formation of Acid Red 92 with trilauryl benzyl ammonium chloride.

(Preparation salt product (A-7A))

By the following procedure, C.I. (A-7A) comprising Acid Red 388 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 388 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-7A) which was a product salt of the salt of Acid Red 388 with distearyldimethylammonium chloride.

(Preparation salt product (A-8A))

By the following procedure, C.I. (A-8A) comprising Acid Red 289 and dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride (Arquad 2HT-75) (molecular weight of the cation part is 438 to 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. After heating the solution to 70 to 90 캜, Arquad 2HT-75 was added dropwise to the solution. Arquad 2HT-75 may be used as an aqueous solution. After completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. To obtain a crude product (A-8A) which is the product of the salt formation of Acid Red 289 with dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride.

(Preparation salt product (A-9A))

By the following procedure, C.I. (A-9A) comprising Acid Red 52 and dimethyl ammonium chloride (Arquad 2HT-75 having a molecular weight of 438 to 550 in the cation part) having dialkyl (the number of the alkyl group of 14 to 18).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. To thereby dissolve the acid red 52, and this solution was sufficiently stirred. After heating the solution to 70 to 90 캜, Arquad 2HT-75 was added dropwise to the solution. Arquad 2HT-75 may be used as an aqueous solution. After completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-9A) which is a product salt of the salt of an acid red 52 with dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride.

(Salt formation product (A-10A))

By the following procedure, C.I. (A-10A) comprising Acid Red 289 and monolauryltrimethylammonium chloride (molecular weight of the cation portion was 228) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and monolauryltrimethylammonium chloride was added dropwise thereto. Monolauryl trimethyl ammonium chloride may be used as an aqueous solution. After completion of dropwise addition of monolauryltrimethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-10A) which is a product salt product of Acid Red 289 and monolauryltrimethylammonium chloride.

(Preparation salt product (A-11A))

By the following procedure, C.I. (A-11A) comprising Acid Red 289 and tetraethylammonium chloride (molecular weight of the cation portion is 122) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and tetraethylammonium chloride was added dropwise thereto. Tetraethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of tetraethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-11A) which was a product salt of the salt of Acid Red 289 with tetraethylammonium chloride.

&Lt; Method for producing xanthan family compound >

(Xanthene compound (C-1A))

C.I. Acid red 289 is sulfonyl chloride formed by the conventional method, and further reacted with a theoretical equivalent amount of dodecylamine in dioxane to give C.I. Thereby obtaining a xanthene-based compound (C-1A) which is a sulfonamide compound of Acid Red 289 (based on the description in Japanese Patent Laid-open No. 6-194828).

(Xanthene compound (C-2A))

C.I. Acid red 52 is sulfonylated by a conventional method and further reacted with a theoretical equivalent amount of dodecylamine in dioxane to give C.I. Thereby obtaining a xanthene-based compound (C-2A) which is a sulfonamide compound of Acid Red 52 (based on the description in Japanese Patent Laid-Open No. 6-194828).

&Lt; Production method of pigment dispersion >

(Preparation of pigment dispersion (DP-1A)

The following mixture was stirred to homogeneity and dispersed for 5 hours by means of zirconia beads having a diameter of 0.5 mm by means of Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a pigment dispersion (DP-1A).

Blue Fine Pigment 1A (CI Pigment Blue 15: 6): 11.0 parts

Acrylic resin solution 1A: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA 4300" manufactured by Chiba Japan Co., Ltd.): 1.0 part

(Preparation of Pigment Dispersions (DP-2A) to (DP-7A)

Pigment dispersions (DP-2A) to (DP-7A) were prepared in the same manner as in the pigment dispersion (DP-1A) except that the blue fine pigment 1A was changed to the pigment shown in Table 1.

&Lt; Preparation method of a resin solution containing a salt formation product and a resin solution containing a xanthene compound >

(Preparation of a salt solution-containing resin solution (DA-1A)

The following mixture was stirred to homogeneity and then filtered through a filter of 5.0 mu m to obtain a resin solution (DA-1A) containing the salt formation product.

Preparation product (A-1A): 11.0 parts

Acrylic resin solution 1A: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Preparation of Formulation Product-Containing Resin Solution (DA-2A) to (DA-11A)

(DA-2A) to ((DA-1A)) were prepared in the same manner as in the above-described formation product-containing resin solution (DA-1A) except that the reaction product (A- DA-11A).

(Preparation of xanthene-based compound-containing resin solution (DC-1A) and (DC-2A)

(DC-1A) was prepared in the same manner as in the above-described formation product containing resin solution (DA-1A), except that the crude product (A-1A) was changed to the xanthene- And (DC-2A) were prepared.

&Lt; Preparation method of red and green resist material >

(Preparation of red resist material)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain a red resist material.

Pigment dispersion (DP-4A): 50.0 parts

Pigment dispersion (DP-5A): 10.0 parts

Acrylic resin solution 1A: 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku Co., Ltd.)

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain a green resist material.

Pigment dispersion (DP-6A): 45.0 parts

Pigment dispersion (DP-7A): 15.0 parts

Acrylic resin solution 1A: 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku Co., Ltd.)

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1A to 11A and Comparative Examples 1A and 2A]

(Example 1A: Coloring composition (DB-1A))

The following mixture was stirred to homogeneity, and then filtered through a 5.0 탆 filter to obtain a mixed coloring composition (DB-1A).

Salt solution containing resin solution (DA-1A): 2.2 parts

Pigment dispersion (DP-1A): 8.8 parts

Acrylic resin solution 1A: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Examples 2A to 1A and Comparative Examples 1A and 2B: Coloring compositions (DB-2A) to (DB-13A))

Except that the coloring composition (DB-1A) was prepared in the same manner as the coloring composition (DB-1A), except that the salt solution containing resin solution (DA-1) -2A) to (DB-13A) were prepared.

(Foreign Film Test)

The above coloring composition was evaluated for ease of occurrence of coating irregularity due to foreign matter. Specifically, first, the coloring composition was applied on a transparent substrate so that the dry film thickness was about 2.0 占 퐉, and this was heated in an oven at 230 占 폚 for 20 minutes to obtain a test substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five visual fields, the number of observable particles was counted, and the total number of particles was obtained. The results are shown in Table 3.

In Table 3, the meanings of the symbols described in the column of "foreign matter on the coating film" are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

When the total number of particles is less than 20, coating irregularities caused by foreign matters hardly occur. When the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. When the total number of particles is 100 or more, coating unevenness (smudge) due to foreign matter occurs.

The coating film obtained from the coloring compositions (DB-1A) to (DB-11A) had few foreign matters (foreign matter of un-dissolved). On the other hand, the coating films obtained from the coloring compositions (DB-12A) and (DB-12B) had much foreign matters. That is, when a xanthene dye is bathed with a quaternary ammonium compound, excellent performance can be achieved as compared with the case where a functional group of a xanthene dye is substituted.

Excellent performance could be achieved in Examples 1A to 9A as compared with Examples 10A and 11A. The crude product of the colored composition used in Example 10A contained only one alkyl chain having 5 or more carbon atoms in its quaternary ammonium portion. In addition, the preparation product of the colored composition used in Example 11A did not contain any one alkyl chain having 5 or more carbon atoms in its quaternary ammonium moiety. The quenched salt product of the colored composition used in Examples 1A to 9A contained two or more alkyl chains having 5 or more carbon atoms in its quaternary ammonium moiety. Therefore, it is preferable that the quaternary ammonium moiety of the salt formation product contains two or more alkyl chains having 5 or more carbon atoms.

[Examples 12A to 24A and Comparative Examples 3A to 5A]

(Example 12: Resist material (R-1A)) [

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain an alkali development type resist material (R-1A).

Salt solution containing resin solution (DA-1A): 12.0 parts

Pigment dispersion (DP-1A): 48.0 parts

Acrylic resin solution 1A: 11.0 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku Co., Ltd.)

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13A to 24A and Comparative Examples 3A to 5A: Resist materials (R-2A) to (R-16A)

(R-2A) to (R-2A) were prepared in the same manner as in the resist material (R-1A) except that the types and amounts of the colorant-containing resin solution and the pigment dispersion were changed as shown in Table 4. [ -16A). In all of these resist materials, the total amount of the colorant-containing resin solution and the pigment dispersion was 60 parts.

(Examples 25A to 30A: Resist materials (R-17A) to (R-22A)

(R-17A), (R-18A), and (R-18A) were prepared in the same manner as the resist material (R-10A) except that the acrylic resin solution 1A was changed to the acrylic resin solutions 2A, R-19A).

The alkali development type resist materials (R-20A) and (R-21A) were prepared similarly to the resist material (R-11A) except that the acrylic resin solution 1A was changed to acrylic resin solutions 2A, 3A and 4A. And (R-22A), respectively.

(Evaluation of resist material)

A coating film was formed from the resist materials (R-1A) to (R-22A), and the chromaticity, foreign matter amount, heat resistance, light resistance and solvent resistance were examined for each of these coating films by the following methods.

(Foreign Film Test)

The above resist material was evaluated for ease of occurrence of coating irregularity caused by foreign matter. Specifically, first, a resist material was applied on a transparent substrate so that the dry film thickness was about 2.5 占 퐉, and the entire surface of the coated film was exposed with ultraviolet rays. Thereafter, this was heated in an oven at 230 DEG C for 20 minutes and then cooled to obtain an evaluation substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five visual fields, the number of identifiable particles was counted, and the total number of particles was obtained. The results are shown in Table 5.

In Table 5, the meanings of the symbols described in the column of "foreign matter on the coating film" are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

When the total number of particles is less than 20, coating irregularities caused by foreign matters hardly occur. When the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. When the total number of particles is 100 or more, coating unevenness due to foreign matter occurs.

(Evaluation of color characteristics)

A resist material was applied on the glass substrate. Specifically, the above resist material was applied to a film thickness such that the chromaticity under the C light source was x = 0.150, y = 0.060. These substrates were heated at 230 占 폚 for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Table 5 shows the results.

(Coating film heat resistance test)

The resist material was coated on the transparent substrate so that the dry film thickness became about 2.5 占 퐉, and the coating film was exposed to ultraviolet rays through a mask having a predetermined pattern. This coating film was sprayed with an alkali developing solution to remove the uncured portions to form a desired pattern. This was then heated in an oven at 230 占 폚 for 20 minutes. After cooling down, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film under a C light source was measured using a brown spectrophotometer (OSP-SP200 manufactured by Olympus Kogaku Co., Ltd.) . Thereafter, this was provided to a heat resistance test in which the plate was heated in an oven at 250 DEG C for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured.

Using these chromaticity values, the color difference? Eab * was calculated by the following calculation formula. Based on the color difference? Eab *, the heat resistance of the coating film was evaluated in the following four stages.

?:? Eab * is less than 1.5

?:? Eab * is not less than 1.5 and less than 3.0

DELTA: Eab * is not less than 3.0 and less than 5.0

X:? Eab * was 5.0 or more

The results are shown in Table 5.

(Coating light resistance test)

(1), a * (1) and b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.) Quot;). Thereafter, the substrate was placed in a light resistance tester (&quot; SUNTEST CPS + &quot; manufactured by TOYOSEIKI), and left for 500 hours. After removal of the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these chromaticities, the color difference (? Eab *) was calculated in the same manner as in the coating film heat resistance test, and the light resistance of the coating film was evaluated in four steps based on the same standard as the heat resistance. Table 5 shows the results.

(Test for solvent resistance of coating film)

(L * (1), a * (1), b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., ). Subsequently, the substrate was immersed in N-methylpyrrolidone for 30 minutes. (2) (L * (2), a * (2), b * (2)) under a C light source were measured and the chromaticity ), And the solvent resistance of the coating film was evaluated in four steps based on the same criteria as the heat resistance. Table 5 shows the results.

The colored layers obtained from the resist materials (R-1A) to (R-12A) and (R-14A) to (R-19A) exhibited excellent light resistance. The colored layer obtained from the resist material (R-13A) had excellent color characteristics. Further, the coloring layer obtained from the resist material (R-13A) was slightly low in heat resistance, light resistance, and solvent resistance, but had no problem in use for a color filter.

On the other hand, the colored layers obtained from the resist materials (R-14A) and (R-15A) had many foreign matters. The coloring layer obtained from the resist material (R-16) has a lightness Y of (R-1) to Low.

As can be seen from the results obtained for the resist materials (R-17A) to (R-22A), foreign matter on the coating film can be reduced by using an active energy ray curable resin having an ethylene bond.

[Examples 31A to 49A and Comparative Examples 6A to 8A]

(Example 31A: Color filter (CF-1A)) [

A black matrix as a light shielding pattern was formed on a glass substrate, and then a red resist material was applied using a spin coater. The red resist material was applied in such a thickness that the chromaticity under the C light source was x = 0.640, y = 0.330. This coating film was irradiated with ultraviolet rays at an exposure dose of 300 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was subjected to a spraying development using an alkali developing solution composed of an aqueous solution of sodium carbonate of 0.2 mass% to remove unexposed portions, followed by washing with ion-exchanged water. Further, this substrate was heated at 230 占 폚 for 20 minutes to form a red filter segment.

Next, a green resist material was applied to the substrate by the same method as described above. The green resist material was applied to a film thickness such that the chromaticity under the C light source was x = 0.300, y = 0.600. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a green filter segment.

On this substrate, a blue resist material (R-1A) was applied by the same method as described above. The blue resist material (R-1A) was applied in such a thickness that the chromaticity under the C light source was x = 0.150 and y = 0.06. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a blue filter segment. Thus, a color filter CF-1A was obtained.

(Production of liquid crystal display)

An electrode made of indium tin oxide (ITO) was formed on the color filter (CF-1A), and an orientation layer made of polyimide was formed thereon. In addition, a TFT array and a pixel electrode were formed on one surface of a glass substrate prepared separately, and an orientation layer made of polyimide was formed thereon.

Next, on the surface provided with the electrodes of one of the glass substrates, a rim-shaped pattern having a passage communicating between the inside and the outside of the rim was formed by using a sealant. Subsequently, these substrates were stuck together with the spacer beads interposed therebetween such that the electrodes faced each other.

Subsequently, the liquid crystal composition was injected into the internal space of the thus obtained cell from the above passage. After sealing the passageway, a polarizing plate was attached to both sides of the cell to obtain a liquid crystal display panel.

Thereafter, a liquid crystal display was completed by combining a liquid crystal display panel and a backlight unit including a three-wavelength CCFL (cold cathode fluorescent lamp).

(Examples 32A to 49A and Comparative Examples 6A to 8A)

(CF-2A) to (CF-22A) and a liquid crystal display in the same manner as the color filter (CF-1A) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 6 .

(Evaluation of color filters (CF-1A) to (CF-22A)

The color image was displayed on the liquid crystal display and the brightness of the area corresponding to the red, green, and blue filter segments was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Then, the brightness of the white display was obtained from these brightness values. The results are shown in Table 6.

The blue filter segment of the liquid crystal display according to Comparative Example 8A was formed from a resist material containing a copper phthalocyanine pigment and a dioxazine-based pigment. As shown in Table 6, the liquid crystal display according to Examples 31A to 49A can display a white image with higher brightness as compared with the liquid crystal display according to Comparative Example 8A.

Further, the liquid crystal display according to Comparative Examples 6A and 7A can display a white image with high brightness. However, as described above, the resist materials used in Comparative Examples 6A and 7A are not practical because they generate many foreign substances in the filter segments.

(Example 50A)

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 mu m to obtain an alkali development type resist material (R-50A).

Salt solution containing resin solution (DA-1A): 12.0 parts

Pigment dispersion (DP-1A): 48.0 parts

Acrylic resin solution 1A: 10.5 parts

Trimethylolpropane triacrylate: 4.2 parts

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku Co., Ltd.)

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Antioxidant pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]: 0.5 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

This resist material (R-50A) was evaluated in the same manner as the resist material (R-1A) and the like. As a result, the lightness Y was 6.9, and excellent performance (?) Was achieved for all of the coating film, heat resistance, light resistance and solvent resistance. That is, the brightness was improved by the use of the antioxidant.

○ Second sun

Next, the second aspect will be described.

The blue coloring composition for a color filter according to the second aspect contains a binder resin, a colorant and an amine compound of copper phthalocyanine. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed from a compound having a cationic group and a xanthene acid dye.

When the blue coloring composition according to the second aspect is used in the production of a color filter, it becomes possible to realize a high brightness and a wide color reproduction area, and excellent performance can be achieved also for heat resistance and light resistance. In addition, when this blue coloring composition is used in the production of a color filter, generation of fluorescence can be suppressed, and therefore, a high contrast ratio can be realized. This blue coloring composition is particularly suitable for use in blue filter segments.

As described above, the transmission spectrum of a blue coloring composition for a color filter, in which a conventional copper phthalocyanine blue pigment and a dioxazine-based pigment are combined, has a peak position in the vicinity of 450 nm and a transmittance in a short wavelength side of 450 nm or shorter have.

On the other hand, in the blue coloring composition for a color filter according to this embodiment, fluorescence is suppressed in the region of 550 to 650 nm. This blue coloring composition achieves a high transmittance at a short wavelength side of 450 nm or less and has a higher transmittance at 450 nm as compared with a blue coloring composition comprising a copper phthalocyanine blue pigment and a dioxazine pigment.

The emission spectrum of a backlight such as a cold cathode tube has a peak wavelength in or near the wavelength range of, for example, 425 to 440 nm. The emission spectrum of a backlight such as a light-emitting diode has a peak wavelength in a wavelength range of, for example, about 450 nm.

Therefore, the filter segment obtained from the coloring composition for a color filter according to the present embodiment can achieve a high brightness and a high contrast ratio.

"coloring agent"

The coloring agent of the blue coloring composition for a color filter according to the present invention contains a preparation of a salt comprising a compound having a xanthene acid dye and a cationic group, and a blue pigment.

By using the blue pigment in combination with the xanthene acid dye, a high transmittance can be achieved within or near the wavelength range of 425 to 500 nm as described above. Therefore, it is possible to realize high brightness and wide color reproduction as compared with the conventional filter segment in which a copper phthalocyanine-based pigment and a dioxazine-based pigment are combined.

<Blue pigment>

As the blue pigment, for example, those described in the first aspect can be used.

<Other Pigments>

As in the first embodiment, other organic pigments can be added to the blue coloring composition of the present invention as long as they do not hinder the obtaining of the effect. As this organic pigment, for example, those described in the first aspect can be used.

[Minification of Pigment]

The blue pigment used in the blue coloring composition of the present invention and other pigments optionally used can be finely ground by a salt milling treatment in the same manner as in the first aspect. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of good dispersion in the colorant carrier. The primary particle diameter of the pigment is preferably 100 nm or less in that a filter segment having a high contrast ratio can be formed. A particularly preferable range is 25 to 85 nm.

The diameter of the primary particles of the pigment is determined from an electron microscope photograph of the pigment by a TEM (transmission electron microscope). Specifically, first, pigment particles are sampled on a grid mesh to prepare a sample for TEM observation. Subsequently, this sample is observed by TEM, and the minor axis diameter and the major axis diameter of the primary particle are measured for each of 100 or more pigment particles. And, the average of them is set as the primary particle diameter of the pigment particle.

<Xanthan Acid Dye>

Suitable xanthene acid dyes according to the present invention exhibit red to purple color, and have either an acidic dye or a direct dye.

The xanthene-based acid dyes exhibiting red to purple color belong to acid dyes such as CI acid red and CI acid violet, or direct dyes such as CI direct red and CI direct violet. Here, since the direct dye has a sulfonic acid group (-SO ₃ H, -SO ₃ Na) in its structure, it is assumed to be an example of the acid dye in this embodiment.

As the acid dye of the xanthene dye, for example, those described in the first aspect can be used. Among xanthene acid dyes, rhodamine dyes are particularly preferable because of their excellent coloring and resistance.

The xanthene acid dye used in this embodiment has a transmittance of not less than 90% for light having a wavelength of 650 nm, a transmittance of not less than 75% for light having a wavelength of 600 nm, a transmittance of not more than 5% And a transmittance of 70% or more with respect to light having a wavelength of 400 nm. More preferably, it is more preferable that the transmittance is 95% or more for light having a wavelength of 650 nm, the transmittance is 80% or more for a light having a wavelength of 600 nm, the transmittance is 10% or less for light having a wavelength of 550 nm, The transmittance is 75% or more.

In addition, the xanthene acid dye has a spectral characteristic having a high transmittance in a wavelength range of 400 to 450 nm. That is, the xanthene acid dye has good spectral characteristics. However, the xanthene-based acid dye lacks light resistance and heat resistance in the same manner as a general dye, and therefore its characteristics are not sufficient for use in an image display in which high reliability is required for a color filter. Therefore, in order to remedy the defects in these dyes, it is preferable to use the xanthene acid dyes in the form of a salt-forming product with quaternary ammonium compounds, tertiary amines, secondary amines or primary amines . It is particularly preferred that the xanthene acid dye is used in the form of a salt-forming product with a quaternary ammonium compound.

(A salt formation product comprising a xanthene acid dye and a quaternary ammonium compound)

Quaternary ammonium compound

As the quaternary ammonium compound, for example, those described in the first aspect can be used in the same manner as in the first aspect.

· Condensation treatment

The crude product of the xanthene acid dye and the quaternary ammonium compound can be obtained by the same method as described in the first aspect.

Of the salt formation products, in particular, C.I. Acid red 289 and the product of preparation of a salt with a quaternary ammonium compound having a cation moiety having a molecular weight in the range of 350 to 800 are excellent in solvent solubility and achieve excellent heat resistance, light resistance and solvent resistance when used in combination with a blue pigment . The reason why the salt formation product is used in combination with the blue pigment to achieve good performance is that the salt formation product is adsorbed on the blue pigment while being dissolved or dispersed in the solvent. From such a viewpoint, it is preferable that the primary particle diameter of the blue pigment is in the range of 20 to 100 nm.

The amount of the salt formation product of the xanthene acid dye and the quaternary ammonium compound is preferably in the range of 1 to 80 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the blue pigment. If the amount of the salt formation product is less than 1 part by mass, reproducible chromaticity regions become narrow, and if it exceeds 80 parts by mass, desired color may not be obtained.

&Quot; Amine compound (C) of copper phthalocyanine &quot;

When the product of the preparation of a quaternary ammonium compound with a xanthene-based acid dye as a coloring agent is used in combination with a blue pigment, transparency derived from a high solubility of the dye is excellent, A segment is obtained. On the other hand, however, there is a problem that the dye itself emits fluorescence and the contrast ratio is lowered. The main reason is that the luminance of the black display is increased due to the fluorescence.

With respect to a blue coloring composition for a color filter containing only a pigment as a coloring agent, the addition of a copper phthalocyanine compound having an acidic substituent or a copper phthalocyanine compound having a basic substituent for the purpose of improving the contrast due to the improvement in the dispersibility of the blue pigment, Lt; / RTI &gt;

The copper phthalocyanine compound having a substituent described above exhibits a high transmittance in a wavelength range of 400 to 450 nm and is therefore suitable as a component added to the blue coloring composition. However, when a xanthene dye capable of becoming more highly visible is used together with a blue pigment, there arises a problem that the contrast ratio is lowered due to fluorescence emission of the xanthene dye. In the case of using a copper phthalocyanine compound having an acid-labile substituent at the terminal (for example, a sulfonic acid compound of copper phthalocyanine), the effect of solving this problem has not been found.

The inventors of the present invention have conducted studies to solve the problem of the contrast reduction due to the fluorescence emission. As a result, the inventors of the present invention found that by using the amine compound (C) of copper phthalocyanine, which will be described later in detail, in addition to the coloring agent containing the blue pigment and the "preparation product of the quaternary ammonium compound and the quaternary ammonium compound" It has been found out that the influence of the fluorescence of the dye on the display is eliminated, that is, the luminance at the time of black display can be lowered, and high contrast can be realized.

The reason why the fluorescent quenching effect becomes remarkable when these materials are used is not clear, but the present inventors consider the following. The amine compound (C) of copper phthalocyanine has high compatibility with xanthene dyes and copper phthalocyanine pigments, and therefore has high efficiency of fluorescence quenching. In particular, since the copper phthalocyanine sulfonic acid amide compound easily forms a charge transfer complex with the xanthene dye, the above effect can be obtained and the fluorescence emission itself can be effectively suppressed. As a result, an extremely high fluorescence extinction effect can be obtained. Further, when the copper phthalocyanine sulfonic acid amide compound is used in addition to the light extinction effect of the fluorescence, since the dye and the copper phthalocyanine blue pigment exhibit high compatibility, the light scattering due to the ubiquination of copper phthalocyanine particles and dyes in the resist . As a result, the luminance at the time of black display is extremely low, and a very high contrast ratio can be achieved.

Examples of the amine compound (C) of copper phthalocyanine include a basic compound having a basic substituent (a copper phthalocyanine sulfonic acid amide compound), a product salt of a salt with an acidic substituent and a quaternary ammonium salt (copper phthalocyanine sulfonic acid ammonium salt) And a phthalimido methyl group may be introduced. This will be described in detail below.

As the amine compound (C) of the copper phthalocyanine used in the present invention, a basic compound in which the copper phthalocyanine pigment has a basic substituent, in particular, an ammonium salt of copper phthalocyanine sulfonate, a copper phthalocyanine tertiary amine, or a copper phthalocyanine sulfonate amide compound is preferable.

Specifically, the amine compound (C) of copper phthalocyanine represented by the following general formula (4) can be suitably used.

In general formula (4):

P-Lm

Wherein P is an m-valent copper phthalocyanine pigment residue, m is an integer of 1 to 4, and L is any one selected from the group consisting of substituents represented by the general formulas (5) to (7) .]

The general formula (5)

In general formula (6):

(7): &lt; EMI ID =

[Among the general formulas (5) to (7)

X _{is, -SO 2 -, -CO-, -CH} 2 -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2 -, or a direct bond,

Y ⁰ is -NH-, -O-, or a direct bond,

n is an integer of 1 to 10,

Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ - or a direct bond,

R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,

Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 1 to 20 carbon atoms.

R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ² are combined to form a nitrogen, oxygen, or sulfur atom Further comprising a heterocyclic ring,

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms ,

R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,

R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6)

Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6).

Examples of the amine component used for forming the substituents represented by the general formulas (5) to (7) include dimethylamine, diethylamine, methylethylamine, N, N- ethylisopropylamine, N, N N, N-dimethylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N Butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisooamylamine, dihexylamine, diisobutylamine, N, N-dimethyloctylamine, N, N-dimethyloctylamine, dicyclohexylamine, diallyl amine, N, , N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, Amine, N, N-diethylaminoethyl N, N-diethylaminopropylamine, N, N-diethylaminobutylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, Amines such as N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, Aminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, 2-piperidinone, 3-piperidinone, 3-piperazinemethanol, piperazinic acid, iso 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4- (4-hydroxyphenyl) propionic acid, isophthalic acid, Piperidine, piperidine, piperacoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N- N-methylpiperazine, N-methylpiperazine, N-methyl homopiperazine, 1-cyclopentylpiperazine, N-methylpiperazine, 1-amino-4-methylpiperazine, and 1-cyclopentylpiperazine.

Amine compounds of copper phthalocyanine having a basic substituent can be synthesized by various synthetic routes. For example, it is possible to introduce any one of the substituents represented by the following formulas (8) to (11) into copper phthalocyanine and then form a substituent represented by the general formulas (5) to (7) Amine compounds such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) , 3,5-triazin-2-ylamino] aniline.

Equation (8): -SO ₂ Cl

Equation (9): -COCl

Equation _{(10): -CH 2 NHCOCH 2} Cl

Formula (11): -CH ₂ Cl

In the reaction of the substituents of the formulas (8) to (11) with the amine component, some of the substituents of the formulas (8) to (11) may be hydrolyzed to replace the chlorine with a hydroxyl group. In this case, the substituents in the formulas (8) and (9) are respectively a sulfonic acid group and a carboxylic acid group, but they may be free acid groups or may be salts with a monovalent trivalent metal or monoamine.

The substituent represented by the general formula (7) can be synthesized by various synthetic routes. For example, an amine component which uses cyanuric chloride as a starting material and forms a substituent represented by the general formula (5) or (6) in at least one chlorine of cyanuric chloride, such as N, N-dimethyl Aminopropylamine or N-methylpiperazine, followed by reacting the remaining chlorine of cyanuric chloride with various amines, alcohols or the like.

The most preferred form of an amine compound of copper phthalocyanine used in the present invention is a copper phthalocyanine sulfonic acid amide compound which is a copper phthalocyanine basic compound.

The copper phthalocyanine sulfonic acid amide compound means a copper phthalocyanine sulfonic acid amide compound having a basic substituent group,

And, - X is -SO ₂ - or -CH ₂ NHSO ₂ CH ₂

Y ⁰ is -NH- or a direct bond,

n is an integer of 1 to 10,

Y ¹ is -NH- or -NR ⁹ -Z-NR ¹⁰ -.

(Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is an alkyl group having 1 to 20 carbon atoms Preferably an alkylene group having 1 to 10 carbon atoms or an arylene group having 1 to 20 carbon atoms, preferably an arylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group And a phenylene group.)

The amine compound (C) of copper phthalocyanine used in this embodiment may be used alone or in combination of two or more.

The blending amount of the amine compound (C) of copper phthalocyanine used in this embodiment is preferably in the range of 0.01 to 200 parts by mass from the viewpoint of the quantitative yield and solubility of fluorescence in the dye when the total amount of the colorant is 100 parts by mass And more preferably in the range of 1 to 100 parts by mass.

In the colorant composition of the present embodiment, the mass ratio of the amine compound (C) of copper phthalocyanine to the &quot; product salt of a quaternary ammonium compound with a quaternary acid dye &quot; (mass of amine compound (C) / &quot; And the product of the salt formation with the quaternary ammonium compound &quot;) is preferably 0.3 to 1.5. If it is less than 0.3, the contrast is lowered because of the suppression of fluorescence and the insufficient dispersion of the amine compound (C) of copper phthalocyanine. When the ratio exceeds 1.5, the color characteristic is affected and becomes prominent. A more preferable mass ratio is 0.4 to 1.2, and a most preferable mass ratio is 0.5 to 1.1.

&Quot; Resin (B) &quot;

The resin is used for dispersing, dyeing and impregnating the colorant, and the resin described in the first aspect can be used in the same manner, and thermoplastic resin, thermosetting resin and the like can be given. In addition to the main resin, rosin ester may be used as the auxiliary resin. That is, the resin (B) is composed of a main resin and an optional auxiliary resin.

[Thermoplastic resin]

As the thermoplastic resin, those described in the first aspect can be used in the same manner. It is preferable to use the method (a) or (b) described in the first aspect.

[Thermosetting resin]

Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a melamine resin, a urea resin, and a phenol resin in the same manner as in the first embodiment.

[Rosin ester]

As described above, the coloring composition according to this embodiment may contain rosin ester as an auxiliary resin for the purpose of improving the dispersibility of the pigment and improving and maintaining the resistance of the xanthene dye, in addition to the above-mentioned resin.

Examples of the rosin ester include rosin derived from rosin, rosin rosin mainly containing abietic acid, neoabietic acid, levopimaric acid, hydroabietric acid, pimaric acid, dexlropimaric acid, (Glycerin ester, pentaerythritol ester, diethylene glycol ester and the like, particularly preferably pentaerythritol ester (e.g., pentaerythritol ester), and the like, with polyhydric alcohols of wood rosin, disproportionated rosin, hydrogenated rosin, partially disproportionated rosin, )to be.

The rosin ester which can be used in the present invention can be obtained, for example, by the following method.

A rosin ester is obtained by using a purified rosin such as purified rosin, purified wood rosin, purified rosin, refined rosin, and purified tall oil rosin as a starting material and esterifying it with an alcohol. In the esterification reaction, usual conditions can be adopted as they are. For example, this esterification reaction is carried out by reacting the purified rosin with the following alcohol under heating in an inert gas stream, for example, while heating at 150 to 300 占 폚 to remove the produced water from the system.

The alcohol component used in the esterification is not particularly limited, and examples thereof include monohydric alcohols such as n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol and lauryl alcohol; Dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol and cyclohexanedimethanol; Trihydric alcohols such as glycerin, trimethylolethane and trimethylolpropane; And tetravalent alcohols such as pentaerythritol and diglycerin. Among them, trivalent or tetravalent polyhydric alcohols are preferably used. These may be used singly or in combination of two or more.

If necessary, an esterification catalyst or an antioxidant may be used. Examples of the esterification catalyst include acid catalysts such as acetic acid and para-toluenesulfonic acid, hydroxides of alkali metals such as calcium hydroxide, and metal oxides such as calcium oxide and magnesium oxide.

As commercially available rosin esters that can be used, for example, the following can be mentioned.

(Rosin ester)

AES, AAL, A, AAV, 105, HS, AT, etc., which are manufactured by Arakawa Kagaku Kogyo Co.,

NL, S, P, C, DS-70L, DS-90, DS-130 and the like, such as neotol G2, 101K, NT-15, 125HK, Harisarase TF,

(Polymerized rosin ester)

PENCEL D-125, D-135 and D-160 manufactured by Arakawa Kagaku Kogyo Co.,

Hariester KT-2 made by Harima Kase.

(Disproportionated rosin ester)

Super Aester A-75, A-100, A-115, -125, and T-125 manufactured by Arakawa Kagaku Kogyo Co.,

(Rosin-modified maleic acid resin, rosin-modified fumaric acid resin)

Arakawa Kagaku Kogyo Co., Ltd. Horse Kid NO. 1, 2, 5, 6, 8, 30A, 31, 32, 33, 34,

R-120, R-100, M-453, M-130A, 135GN, 145P, R-120AH and the like (hydrogenated rosin esters) manufactured by Harima Kasei.

Ester gum H manufactured by Arakawa Kagaku Kogyo Co., Ltd., HP, HD and the like.

Among them, it is preferable to use polymerized rosin ester, disproportionated rosin ester, or rosin-modified maleic acid resin (including rosin-modified fumaric acid resin).

The rosin ester used in this embodiment preferably has an acid value of 100 mg KOH / g or less. More preferably, the rosin ester has an acid value of 40 mg KOH / g or less. The acid value is particularly preferably in the range of 5 to 40 mgKOH / g. Within this range, the acid value is effective for maintaining the performance of the xanthene acid dye.

In consideration of compatibility with the main resin, storage stability, and productivity, the softening point of the rosin ester by the ring method is preferably in the range of 70 to 150 ° C. When the temperature is lower than 70 ° C, the storage stability is lowered, and the blue coloring composition tends to aggregate. If it exceeds 150 ° C, the adhesion of the color filter is deteriorated. Here, the main resin is the above-mentioned thermoplastic resin and / or thermosetting resin.

The addition amount of the rosin ester is preferably 0.3 to 5 parts by mass relative to 100 parts by mass of the main resin. If the amount of the rosin ester added is less than 0.3 part by mass, the effect may not be obtained. If the addition amount is more than 5 parts by mass, there is a possibility that the performance of the resin may be adversely affected.

"solvent"

In the blue coloring composition of the present embodiment, the coloring agent is sufficiently dispersed and penetrated into the coloring agent carrier to form a filter segment on the substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm Solvents may be included for ease of handling.

As the solvent, the same ones as those of the first aspect can be used.

Among them, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, benzyl acetates such as benzyl alcohol, and the like are preferable from the viewpoint of good dispersibility, solubility, It is preferable to use aromatic alcohols such as alcohol or ketones such as cyclohexanone. Among them, it is preferable to use cyclohexanone.

"Dispersion"

The blue coloring composition of the present embodiment is obtained by adding a colorant to a coloring agent carrier composed of a resin (B), an amine compound (C) of copper phthalocyanine and a solvent to be used as required, in a three roll mill, two roll mill, sand mill, Or the like by using various dispersing means. The blue coloring composition of the present invention may be prepared by mixing several kinds of coloring agents each dispersed in a coloring agent carrier.

[Dispersion aid]

When the colorant (A) is dispersed in the colorant carrier, a dispersion aid such as a resin type dispersant and a surfactant can be suitably used in the same manner as in the first aspect. The dispersing aid is excellent in the ability to disperse the pigment component in the coloring agent and has a great effect of preventing re-aggregation of the coloring agent after dispersion. Therefore, when a blue coloring composition obtained by dispersing a coloring agent in a coloring agent carrier using a dispersing aid is used, a color filter having a high spectral transmittance can be obtained.

The blue coloring composition of the present embodiment can be used as a photosensitive blue coloring composition (blue resist material) for a color filter by further adding a photopolymerizable compound and / or a photopolymerization initiator.

&Quot; Photopolymerizable compound &quot;

In this embodiment, for example, the photopolymerizable compound described in the first aspect can be used in the same manner as in the first aspect.

&Quot; Photopolymerization initiator &quot;

When the filter segment is formed by the photolithography method in which the composition is cured by ultraviolet irradiation, the blue coloring composition for a color filter of the present invention may be prepared by adding a photopolymerization initiator or the like to a solvent developing type or an alkali developing type It can be adjusted in the form of a colored resist material.

&Quot;

The blue coloring composition for a color filter of this embodiment can further contain a sensitizer in the same manner as in the first embodiment.

&Quot; Oxygen Reducing Amine Compound &quot;

The blue coloring composition of the present embodiment may contain an oxygen-reduced amine compound having an action of reducing dissolved oxygen.

Examples of such oxygen-reduced amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethyl para-toluidine.

&Quot; Leveling agent &quot;

To improve the leveling property of the composition on the transparent substrate, the leveling agent is preferably added to the blue coloring composition of this embodiment in the same manner as in the first aspect.

&Quot; Hardener, hardening accelerator &quot;

The blue coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary in order to assist curing of the thermosetting resin, as in the first embodiment.

&Quot; Other additive components &quot;

In the blue coloring composition of the present embodiment, a storage stabilizer may be contained in the same manner as in the first embodiment in order to keep the viscosity of the composition substantially constant over a long period of time. Further, in order to improve the adhesion with the transparent substrate, the adhesion improving agent such as a silane coupling agent may be contained in the same manner as in the first aspect.

<< Antioxidants >>

The blue coloring composition of the present invention preferably contains an antioxidant in the same manner as in the first aspect in order to increase the transmittance of the coating film.

&Quot; Preparation of Photosensitive Blue Coloring Composition &quot;

The blue coloring composition for a color filter of the present invention, when used as a photosensitive blue coloring composition in the form of a solvent-developing type or an alkali developing type coloring resist material, can be produced, for example, by mixing a blue pigment and a compound having a cationic group with a xanthene acid dye And a colorant carrier containing a resin (B), an amine compound (C) of copper phthalocyanine and an organic solvent to be used, if necessary, in a 3 roll mill, a 2 roll mill, a sand mill, a kneader, And an open roll type continuous kneader to prepare a blue coloring composition. To this blue coloring composition, a photopolymerizable compound, a photopolymerization initiator, and other resins and solvents used as needed , A dispersant, an additive, and the like.

"Removal of Coarse Particles"

From the blue coloring composition for a color filter of the present invention, coarse particles of 5 mu m or more, preferably coarse particles of 1 mu m or more, more preferably coarse particles of 0.5 mu m or more, It is desirable to remove the dust. Thus, it is preferable that the blue coloring composition for a color filter does not substantially contain particles of 0.5 mu m or more. More preferably, all the particles are substantially 0.3 mu m or less. These particle diameters are values obtained by measurement using a particle size distribution measuring apparatus "Nano-S (Sysmex Corporation)" using a dynamic light scattering method.

"Color filter"

The color filter of the present embodiment includes, for example, at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one blue filter segment is a color filter Lt; / RTI &gt; coloring composition.

The red filter segment can be formed by using a conventional red coloring composition including a red pigment and a pigment carrier in the same manner as in the first embodiment. In the red coloring composition, an orange color pigment and / or a yellow color pigment may be used together in the same manner as in the first aspect.

The green filter segment can be formed by using a conventional green coloring composition including a green pigment and a pigment carrier in the same manner as in the first embodiment.

In the green coloring composition, yellow pigments can be used in combination as in the first embodiment.

&Quot; Method of manufacturing color filter &quot;

The color filter of the present embodiment, like the first aspect,

Can be produced by photolithography.

(Example B)

Hereinafter, this embodiment will be described on the basis of embodiments, but the present invention is not limited thereto. Unless otherwise specified, &quot; part &quot; means &quot; part by mass &quot;.

First, the acrylic resin solution, the colorant (xanthene dye and finely divided pigment), the pigment dispersion, the dye-containing resin solution, the amine compound (C) of copper phthalocyanine and the red and / A method of manufacturing a green resist material will be described.

Here, the weight average molecular weight (Mw) of the acrylic resin is the weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation). Tetrahydrofuran (THF) was used as a developing solvent.

The fineness of the pigment was evaluated by the specific surface area of the pigment particle and the average primary particle diameter. The specific surface area was measured by a BET (Brunauer-Emmett-Teller) method using nitrogen adsorption using an automatic vapor adsorption amount measuring device ("BELSORP18" manufactured by Nippon Bell Co., Ltd.). The contrast ratio of the coated film was measured by the following method.

(Measurement method of contrast ratio of coating film)

The light emitted from the backlight unit for liquid crystal display is incident on the first polarizing plate and the linearly polarized light transmitted through the first polarizing plate is transmitted through the dried coating film of the coloring composition and is made incident on the second polarizing plate. When the transmission axes of the first and second polarizing plates are parallel to each other (corresponding to white display) and the transmission axes of the first and second polarizing plates are orthogonal to each other ). The contrast ratio is a ratio of the luminance when the transmission axes of the first and second polarizing plates are parallel to the luminance when the transmission axes thereof are orthogonal.

Here, a color luminance meter (BM-5A, Topcon Co.) is used as the luminance meter, and "NPF-G1220DUN" manufactured by Nitto Denko Co., Ltd. is used as the first and second polarizers. To measure the luminance, a black mask having holes having a length of 1 cm and a length of 1 cm is superimposed on the second polarizing plate so as to block unwanted light, and the measurement is performed with respect to the area corresponding to this hole.

Further, the linearly polarized light changes to elliptically polarized light when it is scattered by, for example, pigment particles when it passes through the dried coating film of the colored composition. As a result, when the transmission axes of the first and second polarizing plates are parallel, the amount of light transmitted through the second polarizing plate is reduced, that is, when scattering occurs due to the pigment in the coating film, the luminance when the transmission axes are parallel decreases, Since the brightness when the axes are orthogonal increases, the contrast ratio is lowered.

&Lt; Process for producing acrylic resin solutions 1B to 4B >

(Preparation of acrylic resin solution 1B)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer were attached to a separate four-necked flask, and 69.4 parts of cyclohexanone was added to the reaction vessel. After the temperature was raised to 80 ° C and the inside of the reaction vessel was purged with nitrogen, a dropping tube was charged with 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, , 7.4 parts of 2,2'-azobisisobutyronitrile (Aronix M110 manufactured by Toagosei Co., Ltd.) and 0.4 part of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26000. Thereafter, 0.6 part of polymerized rosin ester "PENCEL D-125" (manufactured by Arakawa Chemical Industries, Ltd.) was added to this solution, and the mixture was stirred at 80 ° C for 30 minutes.

After cooling the resin solution to room temperature, about 2 g thereof was sampled. This was dried by heating at 180 캜 for 20 minutes, and the nonvolatile content was measured. On the basis of the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 1B.

(Preparation of acrylic resin solution 2B)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer were attached to a separate four-necked flask, and 205 parts of cyclohexanone was added to the reaction vessel. After the inside of the flask was purged with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, , 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution.

Next, the supply of the nitrogen gas was stopped, and dry air was injected for one hour while stirring with respect to the total amount of the copolymer solution. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Carlen MOI, manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was stirred at 70 ° C for 3 hours . Thereafter, 2.0 parts of polymerized rosin ester "PENCEL D-125" (manufactured by Arakawa Chemical Industries, Ltd.) was added to this solution, and the mixture was stirred at 80 ° C for 30 minutes.

After cooling the resin solution to room temperature, about 2 g thereof was sampled. This was dried by heating at 180 DEG C for 20 minutes, and the amount of nonvolatile matter was measured. Based on the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so as to have a nonvolatile content of 20 mass%, to prepare an acrylic resin solution 2B. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 2B was 18,000.

(Preparation of acrylic resin solution 3B)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube and a stirrer were attached to a separate four-necked flask, and 207 parts of cyclohexanone was added to the reaction vessel. After the inside of the flask was purged with nitrogen, 20 parts of methacrylic acid, 20 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropwise addition, the reaction was continued for 3 hours to obtain a copolymer resin solution.

Then, the supply of the nitrogen gas was stopped, and dry air was injected for one hour while stirring with respect to the total amount of the copolymer solution. Thereafter, the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate, 0.08 parts of dibutyl tin dilaurate and 26 parts of cyclohexanone was added dropwise at 70 占 폚 over 3 hours. Thereafter, 2.0 parts of polymerized rosin ester "PENCEL D-125" (manufactured by Arakawa Chemical Industries, Ltd.) was added to this solution, and the mixture was stirred at 80 ° C for 30 minutes.

After cooling the resin solution to room temperature, about 2 g thereof was sampled. This was dried by heating at 180 DEG C for 20 minutes to measure the amount of non-volatile components. On the basis of the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20 mass%, to prepare an acrylic resin solution 3B. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 3B was 19,000.

(Preparation of acrylic resin solution 4B)

A thermometer, a cooling tube, a nitrogen gas introducing tube, a dropping tube, and an agitator were attached to a separate four-necked flask, and 370 parts of cyclohexanone was added to the reaction vessel. After the inside of the flask was purged with nitrogen, 18 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 10 parts of glycidyl methacrylate , Methyl methacrylate (25 parts) and 2,2'-azobisisobutyronitrile (2.0 parts) was added dropwise over 2 hours. After dropwise addition, the temperature was raised to 100 占 폚, and the reaction was carried out at this temperature for 3 hours. Then, to this solution was added 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 DEG C for 1 hour. Subsequently, 9.3 parts of acrylic acid (100% of glycidyl group), 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were charged into the vessel. The reaction was continued at 120 캜 for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the resulting hydroxyl group) and 0.5 part of triethylamine were added to the thus obtained solution, and the reaction was carried out at 120 占 폚 for 3.5 hours to obtain a solution of the acrylic resin. Thereafter, 2.0 parts of polymerized rosin ester "PENCEL D-125" (manufactured by Arakawa Chemical Industries, Ltd.) was added to this solution, and the mixture was stirred at 80 ° C for 30 minutes.

After cooling the resin solution to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 캜 for 20 minutes to measure the amount of nonvolatile matter. Based on the thus obtained nonvolatile component content, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20 mass%, to prepare an acrylic resin solution 4B. The weight average molecular weight (Mw) of the acrylic resin contained in this resin solution 4B was 19,000.

&Lt; Production method of xanthan series dye >

(Xanthene dye ([A2] -1B): rhodamine-based salt product)

In the following procedure, C.I. ([A2] -1) comprising Acid Red 289 and dialkyl (alkyl C14 to C18) dimethyl ammonium chloride (Arquad 2HT-75) (molecular weight of the cation portion is 438 to 550).

In a sodium hydroxide solution of 7 to 15 mol%, C.I. Acid Red 289 was dissolved and the solution was sufficiently stirred. After heating the solution to 70 to 90 캜, Arquad 2HT-75 was added dropwise to the solution. Arquad 2HT-75 may be used as an aqueous solution. After completion of dropwise addition of Arquad 2HT-75, this solution was stirred at 70 to 90 DEG C for 60 minutes. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. ([A2] -1B), which is the product of the salt formation of Acid Red 289 and dialkyl (alkyl is C14 to C18) dimethyl ammonium chloride.

(Xanthene dye ([A2] -2B): rhodamine based salt product)

By the following procedure, C.I. ([A2] -2B) comprising Acid Red 289 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion is 550) was prepared.

In a sodium hydroxide solution of 7 to 15 mol%, C.I. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 DEG C for 60 minutes. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. ([A2] -2B) which is a product salt of the salt of Acid Red 289 and distearyldimethylammonium chloride.

(Xanthene dye ([A2] -4B): xanthene base salt product)

In the following procedure, C.I. ([A2] -4B) comprising Acid Red 87 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation part is 550) was prepared.

In a sodium hydroxide solution of 7 to 15 mol%, C.I. Acid Red 87 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 DEG C for 60 minutes. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. ([A2] -4B) which is a product salt of the salt of Acid Red 87 and distearyldimethylammonium chloride.

&Lt; Production method of micronized pigment >

(Preparation of blue fine pigment ([A1] -1B)

200 parts of CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a triphenylmethane blue pigment, And kneaded at 80 DEG C over 6 hours. Next, this kneaded product was charged into 8 liters of hot water and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a blue fine pigment ([A1] -1B). The specific surface area of the blue fine pigment ([A1] -1B) was 65 m ² / g, and the average primary particle diameter by TEM observation was 55 nm.

(Preparation of blue fine pigment ([A1] -2B)

200 parts of CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C overnight to obtain 190 parts of a blue fine pigment ([A1] -2B). The specific surface area of the blue fine pigment ([A1] -2B) was 80 m ² / g, and the average primary particle diameter by TEM observation was 50 nm.

(Preparation of red fine pigment)

200 parts of CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Japan Co.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a diketopyrrolopyrrole type red pigment And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of red fine pigment. The specific surface area of the red fine pigment was 65 m ² / g, and the average primary particle diameter by TEM observation was 54 nm.

(Preparation of green fine pigment)

200 parts of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. The filtration and washing were repeated to remove sodium chloride and diethylene glycol, and then dried at 85 ° C for one day and one night to obtain 190 parts of a green fine pigment. The specific surface area of the green fine pigment was 75 m ² / g, and the average primary particle diameter by TEM observation was 51 nm.

(Preparation of Yellow Fine Pigment 1B)

, 500 parts of CI Pigment Yellow 139 ("Irgafour Yellow 2R-CF" manufactured by Chiba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were mixed with a stainless steel first gallon kneader ), And kneaded at 120 DEG C for 8 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to obtain 490 parts of yellow fine pigment 1B. The specific surface area of the yellow fine pigment 1B was 80 m ² / g, and the average primary particle diameter by TEM observation was 49 nm.

(Preparation of yellow fine pigment 2B)

200 parts of CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) Over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of yellow fine pigment 2B. The specific surface area of the yellow fine pigment 2B was 70 m ² / g, and the average primary particle diameter by TEM observation was 53 nm.

(Preparation of purple fine pigment)

200 parts of CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day and one night, to obtain 190 parts of a purple fine pigment. The specific surface area of the purple fine pigment was 95 m ² / g, and the average primary particle diameter by TEM observation was 45 nm.

&Lt; Production method of pigment dispersion >

(Production of pigment dispersion (P-1B)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a pigment dispersion (P-1B).

Blue fine pigment ([A1] -1B) (CI Pigment Blue 1): 11.0 parts

Acrylic resin solution 1B: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Chiba Japan): 1.0 part

(Preparation of Pigment Dispersions (P-2B) to (P-7B)) [

(P-2B) to (P-2B) were prepared in the same manner as in the above pigment dispersion (P-1B) except that the blue fine pigment ([A1] 7B) was prepared.

&Lt; Preparation of dye-containing resin solution >

(Preparation of dye-containing resin solution (DA-1B)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a dye-containing resin solution (DA-1B).

Preparation product 1B: 11.0 parts

Acrylic resin solution 1B: 40.0 parts

Cyclohexanone: 49.0 parts

(Preparation of dye-containing resin solutions (DA-2B) to (DA-4B)

(DA-2B) and (DA-4B) were obtained in the same manner as in the dye-containing resin solution (DA-1B) except that the salt formation product 1B was changed to the xanthene- It was prepared.

&Lt; Preparation method of red and green resist material >

(Preparation of red resist material)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain a red resist material.

Pigment dispersion (P-3B): 50.0 parts

Pigment dispersion (P-5B): 10.0 parts

Acrylic resin solution 1B: 11.0 parts

Trimethylolpropane triacrylate

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain a green resist material.

Pigment dispersion (P-4B): 45.0 parts

Pigment dispersion (P-6B): 15.0 parts

Acrylic resin solution 1B: 11.0 parts

Trimethylolpropane triacrylate

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

&Lt; Process for producing amine compound (C) of copper phthalocyanine &

Commercially available amine compounds (C-1B) and (C-2B) of copper phthalocyanine were used. Table 9 shows specific chemical names and chemical structures.

(Preparation of amine compound (C-3B) of copper phthalocyanine: copper phthalocyanine sulfonic acid amide compound)

30 parts of copper phthalocyanine was added to 300 parts of chlorosulfonic acid, and this was completely dissolved. Then, 24 parts of thionyl chloride was added to this solution, the temperature was gradually raised to 101 ° C, and the reaction was carried out at this temperature for 3 hours. The reaction solution was poured into 9,000 parts of ice water, stirred, filtered and rinsed. The resulting press cake was dispersed in 300 parts of water to prepare a slurry. To this slurry, 15 parts of N, N-dimethylaminopropylamine was added and the mixture was stirred at room temperature for 3 hours and then at 60 DEG C for 2 hours. Thereafter, filtration, washing with water and drying were carried out to obtain 36 parts of copper phthalocyanine sulfonic acid amide compound (E-3). The resulting copper phthalocyanine sulfonic acid amide compound was analyzed by liquid chromatography mass spectrometry platform LCZ manufactured by Waters. As a result, it was confirmed that this product did not contain a compound having three or more substituents, and a copper phthalocyanine sulfonic acid amide compound (C-3B-D1) having one substituent of the following formula (12) And a copper phthalocyanine sulfonic acid amide compound (C-3B-D2) having two substituents at a mass ratio of 85:15.

In general formula (12)

(Preparation of amine compounds (C-4B) to (C-6B) of copper phthalocyanine: copper phthalocyanine sulfonic acid amide compound)

(C-4B) to (C-4B) were prepared in the same manner as in the case of the copper phthalocyanine sulfonic acid amide compound (C-3B), except that N, N-dimethylaminopropylamine was changed to the raw materials shown in Table 9. The copper phthalocyanine sulfonic acid amide 6B) was prepared.

In Table 9, &quot; CuPc &quot; represents a copper phthalocyanine residue. In Table 9, "SOLSPERSE 12000" (manufactured by Nippon Lubrizol Co., Ltd.) is described as the copper phthalocyanine compound (D-1B).

[Examples 1B to 6B and 8B to 15B and Comparative Examples 1B, 2B and 4B]

&Lt; Preparation of blue coloring composition >

(Example 1B: Blue coloring composition (DB-1B))

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a coloring composition (DB-1B) for a color filter.

Dye-containing resin solution (DA-1B): 10.0 parts

Pigment dispersion (P-1B): 50.0 parts

Acrylic resin solution 1B: 11.0 parts

Cyclohexanone: 27.4 parts

Resinous dispersant

(&Quot; EFKA4300 &quot; manufactured by Chiba Japan Co., Ltd.): 1.0 part

The amine compound (C-1B) of copper phthalocyanine

(SOLPERSE 5000 manufactured by Nippon Lubrizol Corporation; ammonium phthalocyanine sulfonate) 0.6 part

(Examples 2B to 6B and 8B to 15B and Comparative Examples 1B, 2B and 4B: Blue coloring compositions (DB-2B) to DB-6B, DB- 8B to DB- ))

The dye-containing resin solution (DA-1B), the pigment dispersion (P-1B) and the amine compound (C-1B) of copper phthalocyanine were mixed with the dye-containing resin solution shown in Table 10, the pigment dispersion and the amine of copper phthalocyanine (DB-2B) to (DB-6B), (DB-8B) to (DB-13B) were obtained in the same manner as in the above-mentioned blue coloring composition (DB-15B). Further, in some blue coloring compositions, two or more kinds of pigment dispersions are used, but the total mass portion of the dye-containing resin solution and the pigment dispersant is 60 parts in all the blue coloring compositions. Table 10 shows the blend of the obtained blue coloring composition.

[Evaluation of blue coloring compositions (DB-1B) to (DB-6B), (DB-8B) to (DB-13B)

Each of the blue coloring compositions DB-1B to DB-6B, DB-8B to DB-13B and DB-15B was changed in thickness from 100 mm × 100 mm to 1.1 mm in thickness The glass substrate was coated with a spin coater. Each blue coloring composition was applied to a film thickness such that the chromaticity under the C light source was y = 0.06. Subsequently, these substrates were heated at 230 占 폚 for 20 minutes to form a blue coloring layer on the substrate. Thereafter, the contrast ratio was determined for each of the substrates on which the colored layer was formed by the above-described method. The results are shown in Table 10.

(Examples 1B to 6B and 8B to 11B) containing the amine compound (C) of copper phthalocyanine were used, a blue coloring composition containing no amine compound (C) of copper phthalocyanine (Comparative Examples 1B and 2B And 4B were used, a high contrast ratio could be achieved. Among them, particularly when a blue coloring composition (DB-3B) to (DB-6B) and (DB-8B) to (DB-11B) containing a copper phthalocyanine sulfonic acid amide compound was used, a particularly high contrast ratio could be achieved.

[Examples 12B to 20B and 23B to 26B and Comparative Examples 5B to 6B and 8B]

&Lt; Preparation of resist material &

(Example 12B: Resist material (R-1B)) [

The following mixture was stirred so as to be homogeneous and then filtered through a filter of 1.0 mu m to obtain a resist material (R-1B).

Blue coloring composition (DB-1B): 60.0 parts

Acrylic resin solution 1B: 11.6 parts

Trimethylolpropane triacrylate

("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 3.6 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Examples 13B to 20B and 23B to 26B and Comparative Examples 5B to 6B and 8B: Resist materials R-2B to R-9B, R-12B to R-17B, )

Except that the blue coloring composition (DB-1B) and the acrylic resin solution 1B were changed to the blue coloring composition and the acrylic resin solution shown in Table 11, respectively, in the same manner as the resist material (R-1B) R-2B) to (R-9B), (R-12B) to (R-17B) and (R-19B). The compositions of these resist materials are shown in Table 11.

Evaluation of resist materials R-1B to R-9B, (R-12B) to (R-17B)

The evaluation of the color characteristics (brightness) and contrast ratio of the resist materials R-1B to R-9B, (R-12B) I did.

(Evaluation of color characteristics)

Each of the above resist materials was coated on a glass substrate with a film thickness such that the chromaticity under the C light source was y = 0.06 and the substrate was heated at 230 占 폚 for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). The results are shown in Table 11.

(Contrast ratio evaluation)

The contrast ratio of each of the substrates on which the colored layer was formed was measured by the above-described method. The results are shown in Table 11.

(Method of coating film heat resistance test)

The resist material was coated on the transparent substrate so that the dry film thickness became about 2.5 占 퐉, and the coating film was exposed to ultraviolet rays through a mask having a predetermined pattern. This coating film was sprayed with an alkali developing solution to remove the uncured portions, thereby forming a desired pattern. This was then heated in an oven at 230 占 폚 for 1 hour. After cooling down, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film under a C light source was measured using a brown spectrophotometer (OSP-SP200 manufactured by Olympus Kogaku Co., Ltd.) . Thereafter, this was provided to a heat resistance test in which the plate was heated in an oven at 250 DEG C for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured.

Using these chromaticity values, the color difference? Eab * was calculated by the following calculation formula. Based on the color difference? Eab *, the heat resistance of the coating film was evaluated in the following four stages.

?:? Eab * is less than 1.5

?:? Eab * is not less than 1.5 and less than 3.0

DELTA: Eab * is not less than 3.0 and less than 5.0

X:? Eab * was 5.0 or more

The results are shown in Table 11.

(R-1B) containing an amine compound (C) of copper phthalocyanine, a colorant containing a blue pigment, a coloring agent containing a salt product of a quaternary ammonium compound and a quaternary ammonium compound, (R-16B), (R-17B), and (R-17B) that do not contain the amine compound (C) of copper phthalocyanine when using (R-9B) R-19B), it was possible to achieve a high contrast ratio. Among them, especially when a resist material (R-3) to (R-9B) and (R-12B) to (R-15B) containing a copper phthalocyanine sulfonic acid amide compound was used, a particularly high contrast ratio could be achieved. This is because the electrostatic attraction between the xanthene dye and the copper phthalocyanine sulfonic acid amide compound acts efficiently to quench the fluorescence of the dye and also the compatibility of the dye with the copper phthalocyanine blue pigment is good and therefore the copper phthalocyanine particles and the dye It is considered that light scattering is suppressed because there is no omnipresence in the resist.

Further, in Example 3B in which the mass ratio of the amine compound (C) of copper phthalocyanine to the "salt product of a quaternary ammonium compound and a quaternary ammonium compound" is within the range of 0.3 to 1.5, the amine compound (C) of copper phthalocyanine The effect on the color characteristics of the blue coating film of the blue color was small. Specifically, in Example 3B, higher brightness could be achieved as compared with Example 4B in which the mass ratio was larger than 1.5. In Example 3B, as compared with Example 5B in which the mass ratio was smaller than 0.3, the ability to suppress fluorescence was excellent, and a higher contrast ratio could be achieved.

In Examples 13B to 20B and 23B to 26B, as the blue pigment, the copper phthalocyanine pigment C.I. Pigment Blue 15: 6 was used. Therefore, in Examples 13B to 20B and 23B to 26B, triarylmethane-based C.I. As compared with Example 12B using Pigment Blue 1, superior heat resistance could be achieved.

On the other hand, in Comparative Example 8B in which fine pigment (C.I. Pigment Violet 23) was used in place of the xanthan dyestuff, a decrease in brightness and a decrease in contrast ratio were confirmed.

With respect to heat resistance, when a rhodamine-based salt formation product is used among the kissantene dyes, heat resistance superior to that in the case of using a xanthene-based dyestuff dye (Example 26B) or a fine pigment (CI Pigment Violet 23) It was confirmed that it could. Also, in Examples 17B to 19B, excellent heat resistance could be achieved. This is presumably because the curing property of the coating film was improved due to the incorporation of an active energy ray curable resin having an ethylene bond in the resin solution.

From these results, it has been found that a resist material using the color composition of the present invention can achieve excellent color characteristics (brightness), high contrast ratio, and heat resistance.

[Examples 27B to 35B and 38B to 41B and Comparative Examples 9B to 10B and 12B]

A color filter was produced using the obtained resist material.

(Example 27B: Color filter (CF-1B)) [

A black matrix as a light shielding pattern was formed on a glass substrate, and then a red resist material was applied using a spin coater. The red resist material was applied so that the chromaticity under the C light source was x = 0.640. This coating film was irradiated with ultraviolet rays at an exposure dose of 300 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was subjected to a spraying development using an alkali developing solution composed of an aqueous solution of sodium carbonate of 0.2 mass% to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was further heated at 230 DEG C for 20 minutes to form a red filter segment.

Next, a green resist material was applied onto the substrate by the same method as described above. The green resist material was applied with a film thickness such that the chromaticity under the C light source was y = 0.600. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a green filter segment.

On this substrate, a blue resist material (R-1B) was applied by the same method as described above. The blue resist material (R-1B) was coated to a film thickness such that the chromaticity under the C light source was y = 0.06. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a blue filter segment. Thus, a color filter CF-1B was obtained.

(Production of liquid crystal display)

An electrode made of ITO was formed on the color filter CF-1B, and an orientation layer made of polyimide was formed thereon. In addition, a TFT array and a pixel electrode were formed on one surface of a glass substrate prepared separately, and an orientation layer made of polyimide was formed thereon.

Next, on the surface of one of the glass substrates on which the electrodes were provided, a sealing agent was used to form a rim-shaped pattern having a passage communicating the inside and the outside of the rim. Subsequently, these substrates were stuck together with the spacer beads interposed therebetween so that the electrodes face each other.

Subsequently, the liquid crystal composition was injected into the internal space of the thus obtained cell from the above passage. After sealing the passageway, a polarizing plate was attached to both sides of the cell to obtain a liquid crystal display panel.

Thereafter, a liquid crystal display was completed by combining a liquid crystal display panel and a backlight unit.

(Examples 28B to 35B and 38B to 41B and Comparative Examples 9B to 10B and 12B: Color Filters CF-2B to CB-9B, CB-12B to CB- )

(CF-2B) to (CB-9B), (CB-12B) and (CB-9B) were prepared in the same manner as the color filter ) To (CB-17B) and (CF-19B) and a liquid crystal display, respectively. Fig. 1 shows the emission spectrum of the backlight used here.

Evaluation of color filters CF-1B to CB-9B, (CB-12B) to (CB-17B) and (CF-

The color image was displayed on the liquid crystal display and the brightness of the area corresponding to the red, green, and blue filter segments was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Then, the brightness of the white display was obtained from these brightness values.

The contrast ratios of the areas corresponding to the red, green and blue filter segments were measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.), and the contrast ratios . The contrast ratio in black and white display is practically required to be 7600 or more, and preferably 7600 or more. Table 12 shows the evaluation results of the color filters.

The blue resist material used in Comparative Examples 9B, 10B, and 12B did not contain the colorant (A) containing the blue pigment [A1], the xanthene dye [A2], and the amine compound (C) of copper phthalocyanine. In Examples 27B to 35B and 38B to 41B, as compared with Comparative Examples 9B, 10B, and 12B, the contrast ratio in black-and-white display was high and practical performance could be achieved. The performance achieved in Comparative Examples 9B and 10B was lower because the blue resist material used in Comparative Examples 9B and 10B did not contain the amine compound (C) of copper phthalocyanine, so that the fluorescence component of the xanthene- And as a result, the luminance at the time of black display is increased. From the results of Comparative Example 12B, it was confirmed that the use of a fine pigment (CI Pigment Violet 23) instead of a rhodamine-based dye or a xanthene-based dye results in further lowering of brightness.

As described above, by using the colorant (A) containing the blue pigment [A1] and the xanthene dye [A2] together with the amine compound (C) of the copper phthalocyanine, it is possible to provide a color filter having excellent color characteristics (brightness), heat resistance and contrast ratio It becomes possible to obtain a blue coloring composition and a color filter.

○ The third sun

Next, the third aspect will be described.

The blue coloring composition for a color filter according to the third aspect contains a binder resin and a colorant. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed of a compound having a cationic group and a xanthene acid dye. In this embodiment, an amine is used as a compound having a cationic group. The amine is at least one selected from the group consisting of a primary amine, a secondary amine, and a tertiary amine.

When the blue coloring composition according to the third aspect is used in the production of a color filter, it becomes possible to realize a high brightness and a broad color reproduction area. Further, since the dye is in the form of a salt formation product, Excellent performance can be achieved.

In addition, the transmission spectrum of a blue coloring composition for a color filter in which a conventional copper phthalocyanine blue pigment and a dioxazine-based pigment are combined has a peak position near 450 nm, and a transmittance sharply decreases on a short wavelength side of 450 nm or shorter.

On the contrary, when the blue coloring composition for a color filter according to the present embodiment is used, a high transmittance is achieved at a short wavelength side of 450 nm or less as compared with the case of using a combination of a copper phthalocyanine blue pigment and a dioxazine-based pigment. Incidentally, the emission spectrum of many backlights such as cold-cathode tubes has a peak wavelength in or near the wavelength range of, for example, 425 to 500 nm. Therefore, the filter segment obtained from the blue coloring composition for a color filter according to the present embodiment can achieve high brightness.

<Colorant>

The coloring agent of the blue coloring composition for a color filter of the present invention comprises a xanthate acid dye and at least one of a salt formation product (A) selected from a primary amine, a secondary amine and a tertiary amine, and a blue pigment.

By using the salt formation product (A) in combination with the blue pigment, a high transmittance can be achieved at or near the wavelength range of 425 to 500 nm as described above. Therefore, it is possible to realize high brightness and wide color reproduction as compared with the conventional color filter in which a copper phthalocyanine pigment and a dioxazine pigment are combined. In addition, it is possible to realize high solvent solubility as well as high heat resistance, light resistance and solvent resistance by controlling the acid dye.

(Preparation salt product (A))

The salt formation product (A) will be described. The xanthene acid dye used in the preparation of a salt (A) comprising a xanthene acid dye and a cation component of a primary amine, a secondary amine or a tertiary amine exhibits red to purple color and has a dye form.

The xanthene-based acid dyes exhibiting red to purple color are C.I. Acid Red and C.I. Acid dyes such as Acid Violet; Direct Red and C.I. Direct violet and the like. Here, the direct dye has a sulfonic acid group, and therefore, it is assumed that it is one form of the acid dye in this embodiment.

The salt formation product (A) belongs to a salt forming dye which is formed by kneading from a xanthene acid dye (including a direct dye) and an amine which is a counter component generating a counter ion, and if necessary, denatured. In this salt-forming reaction, the amine compound exists as an ammonium ion in an aqueous solution and reacts with an acidic dye dissolved in this aqueous solution. Here, an aqueous acetic acid solution is preferably used.

[Xanthane acid dye]

The xanthene acid dye will be described. As the xanthene acid dye, the same one as in the first embodiment can be used.

Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, or C.I. Acid Red 388 is preferably used.

[Amine compound]

Next, the amines which generate the cation component which is the counter ion of the xanthene acid dye will be explained. Since the amine has an amino group, the ion is used as a counter ion of the acid dye.

The amine which is the counter component of the salt formation product (A) is preferably colorless or white.

Here, it is defined as a so-called transparent state in which colorless or white is formed, and the transmittance is defined as 95% or more, preferably 98% or more in the entire wavelength range of 400 to 700 nm which is a visible light region. That is, it is necessary that the amine does not inhibit the color development of the dye component and does not cause the color change.

The amines include primary amines, secondary amines and tertiary amines. Among them, secondary amines or tertiary amines are preferably used because they are excellent in heat resistance and light resistance. Primary amines generally fall behind in performance in comparison to secondary amines and tertiary amines, but are preferred materials, for example, by optimizing the number of carbon atoms in the alkyl group.

The molecular weight of the amine is preferably in the range of 129 to 591, and more preferably in the range of 255 to 591. When the molecular weight is smaller than 129, the light resistance and heat resistance are lowered, and the solubility in a solvent is lowered. When the molecular weight is larger than 591, the proportion of the coloring component in the molecule is lowered, and as a result, the coloring property is lowered and the brightness is lowered. Here, the molecular weight is calculated based on the structural formula. The atomic weight of C is 12, the atomic weight of H is 1, and the atomic weight of N is 14.

Further, the more preferred molecular weights of the primary amine, the secondary amine and the tertiary amine are as follows.

The molecular weight of the primary amine is, for example, in the range of 129 to 297, preferably in the range of 255 to 297. [ When the molecular weight is less than 129, the light resistance and heat resistance are lowered, and the solubility in a solvent is lowered. When the molecular weight is more than 297, the proportion of the coloring component in the molecule is lowered, and the coloring property is lowered and the brightness is also lowered.

The molecular weight of the secondary amine is preferably in the range of, for example, 241 to 577, and preferably in the range of 353 to 577. If the molecular weight is less than 241, the light resistance and heat resistance are lowered, and the solubility in a solvent may be lowered. When the molecular weight is more than 577, the proportion of the coloring component in the molecule is lowered, and the coloring property is lowered and the brightness is also lowered.

The molecular weight of the tertiary amine is preferably in the range of, for example, 255 to 591, and preferably in the range of 311 to 591. If the molecular weight is less than 255, the light resistance and heat resistance are lowered, and the solubility in a solvent may be lowered. When the molecular weight is more than 591, the proportion of the coloring component in the molecule is lowered, and the coloring property is lowered and the brightness is also lowered.

The secondary amine and the tertiary amine are preferably represented by the following general formula (13).

In general formula (13):

R ₁ R ₂ R ₃ N

[In the formula (13), two of R ₁ to R ₃ each independently represent an alkyl group or a benzyl group having 8 to 22 carbon atoms, and one of R ₁ to R ₃ is a hydrogen atom or an alkyl group having 1 to 22 carbon atoms or benzyl Group.]

When two or more of R ₁ to R ₃ are an alkyl group having 8 to 22 carbon atoms or a benzyl group, solubility in a solvent becomes good. More preferably, two or more of R ₁ to R ₃ are an alkyl group or a benzyl group having 12 to 22 carbon atoms. When two alkyl groups having less than 8 carbon atoms are present, solubility in a solvent is deteriorated, and foreign matters on the coating film are liable to be generated. When an alkyl group having more than 22 carbon atoms is present, the color forming property of the salt formation product (A) is impaired. When two groups having 8 to 22 carbon atoms are present, solvent solubility is remarkably improved.

(Primary amine)

The primary amine is represented by the following general formula (14).

In general formula (14):

RNH ₂

Here, R is, for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The primary amine may have an oxygen atom or the like between R and the nitrogen atom.

Examples of the substituent of the aliphatic hydrocarbon group which may have a substituent or the aromatic hydrocarbon group which may have a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, An alkylthio group, an arylthio group, a hydroxy group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a substituted carbamoyl group, a substituted sulfamoyl group, a nitro group, a substituted amino group, an alkylsulfonyl group, an arylsulfonyl group, Group, and a substituted arylsulfoamide group.

Examples of the primary amine include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (Laurylamine), tridodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, Aliphatic unsaturated primary amines such as benzylamine, aniline, and benzylamine.

The number of carbon atoms of the alkyl group constituting the primary amine is preferably in the range of 8 to 24. When the number of carbon atoms is less than 8, it is difficult to dissolve in an organic solvent and high heat resistance and light resistance can not be attained. When the number of carbon atoms is more than 24, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 10 to 20, more preferably in the range of 14 to 20.

Preferred primary amines have a number of carbon atoms greater than or equal to the number of carbon atoms of the octylamine. Such primary amines are usually present as mixtures of compounds with different numbers of carbon atoms. That is, such primary amines have a distribution of the number of carbon atoms. Specific examples thereof include octylamine (the number of carbon atoms is in the range of 8 to 10, and the number of octylamine is 8 in terms of the number of 98%), laurylamine (the number of carbon atoms is in the range of 10 to 14, (98% in terms of the number of carbon atoms), myristylamine (in which the number of carbon atoms is in the range of 12 to 16, and the number in the number of 14 is 96%), stearylamine (in the range of 14 to 20 carbon atoms, (In which the number of carbon atoms is in the range of 12 to 20, and the number of carbon atoms is 18 is 64%), curing alkylamine (in which the number of carbon atoms is in the range of 12 to 20, (Number ratio of carbon atoms is 65 to 65%), and oleylamine (number of carbon atoms is in the range of 14 to 20, and 18 is number ratio is 82%). Among them, it is preferable to use a fatty alkylamine, a hardened alkylamine, oleylamine or stearylamine.

Specific examples of commercially available primary amines include amine 8D (octylamine), amine 12D (laurylamine), amine 14D (myristylamine), amine 18D (stearylamine) (Cyanide), TD (tallow alkylamine), amine HTD (cured urea alkylamine) and amine OD (oleylamine), and Chaosamine Pamine CS (coconut amine), Pamine 08D (octylamine), Pamine 20D Pamine 80 (stearylamine), Pamine 86T (stearylamine), Pamine O (oleylamine) and Pamine T (Ujiamine).

(Secondary amine)

The secondary amine is represented by the following general formula (15).

In general formula (15):

R ₁ R ₂ NH

Herein, R ₁ and R ₂ are, for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The secondary amine may have an oxygen atom or the like between R ₁ or R ₂ and a nitrogen atom.

Examples of the substituent of the aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, An alkylthio group, an arylthio group, a hydroxy group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a substituted carbamoyl group, a substituted sulfamoyl group, a nitro group, a substituted amino group, an alkylsulfonyl group, an arylsulfonyl group, Group, and a substituted arylsulfoamide group. Examples of secondary amines include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, and diallylamine; amines such as methyl aniline, Dibenzylamine, diphenylamine, dicocoalkylamine, di-cured uro-alkylamine, and distearylamine.

Of the groups represented by the general formula (15), it is preferable that R ₁ and R ₂ are an alkyl group having 8 to 22 carbon atoms or a benzyl group. The secondary amine having 8 or more carbon atoms usually exists as a mixture of a compound having a smaller number of carbon atoms and a compound having a larger number of carbon atoms. That is, such a secondary amine usually has a distribution of the number of carbon atoms.

The number of carbon atoms constituting the alkyl group of the secondary amine is preferably in the range of 8 to 22. When the number of carbon atoms is less than 8, it is not dissolved in the organic solvent, and the heat resistance and the light resistance are inferior. When the number of carbon atoms is greater than 22, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 12 to 18, more preferably in the range of 14 to 18.

Examples of secondary amines include dicocoalkylamines having a number of carbon atoms in the range of 8 to 18, with 12 in number ratio of 60%), di-cured urea alkyl amines (having the number of carbon atoms in the range of 12 to 20, 65% by weight) or distearylamine (the number of carbon atoms is in the range of 14 to 18, and the number of carbon atoms is 18, 66%).

Commercially available secondary amines that can be specifically used include, for example, amine 2C and amine 2HT manufactured by Lion, and amine D86 available from Kao Corporation.

(Tertiary amine)

The tertiary amine is represented by the following general formula (16).

In general formula (16):

R ₁ R ₂ R ₃ N

Here, R ₁ to R ₃ are, for example, an aliphatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent. The tertiary amine may have an oxygen atom or the like between each of R ₁ to R ₃ and a nitrogen atom.

Examples of the substituent of the aliphatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which may have a substituent include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, a halogen atom, an acylamino group, An alkylthio group, an arylthio group, a hydroxy group, a cyano group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a substituted carbamoyl group, a substituted sulfamoyl group, a nitro group, a substituted amino group, an alkylsulfonyl group, an arylsulfonyl group, Group, and a substituted arylsulfoamide group.

As the tertiary amine, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, or tribenzylamine can be used. As the tertiary amine, for example, a tertiary amine represented by the following general formula (17) or (18) may be used.

In general formula (17):

RN (CH _{3) 2}

Wherein R is an alkyl or benzyl group having 8 to 22 carbon atoms.

In general formula (18):

R ₁ R ₂ NCH ₃

Wherein R ₁ and R ₂ are an alkyl group or a benzyl group having 8 to 22 carbon atoms.

The tertiary amine having 8 or more carbon atoms usually exists as a mixture of a lower number of carbon atoms and a higher number of carbon atoms. That is, such tertiary amines typically have a distribution of the number of carbon atoms.

The number of carbon atoms constituting the alkyl group of the tertiary amine, particularly the tertiary amine represented by the general formula (17), is preferably in the range of 8 to 22. When the number of carbon atoms is less than 8, it is not dissolved in the organic solvent, and the heat resistance and the light resistance are inferior. When the number of carbon atoms is larger than 22, the coloring power as a dye is lowered. The number of carbon atoms is preferably in the range of 12 to 18, more preferably in the range of 14 to 18.

Examples of the tertiary amine represented by the general formula (17) include N-methyldodecylamine (the number of carbon atoms is in the range of 8 to 12, and the number of carbon atoms is 10 is 98%), Amines (having a number of carbon atoms in the range of 8 to 18, 12 in number ratio of 60% and 14 in number ratio of 22%), N-methyldiglycidoxyalkylmethylamines having 12 to 20 carbon atoms (In which the number of carbon atoms is in the range of 14 to 20 and the number of carbon atoms is 18, the number ratio is 84%), and Diracl And monomethylamine (the number of carbon atoms is in the range of 10 to 14, and the number of carbon atoms is 98% in number).

Examples of the tertiary amine represented by the general formula (18) include N, N-dimethyl laurylamine (the number of carbon atoms is in the range of 10 to 14, Dimethylmyristylamine (having a number of carbon atoms in the range of 12 to 16, with 14 in number ratio of 96%), N, N-dimethylphthalimylamine (having a number of carbon atoms in the range of 14 to 18, N, N-dimethylstearylamine (having a number of carbon atoms in the range of 14 to 20, and a number of 18 in terms of number ratio of 94%), N, N-dimethylbehenylamine N, N-dimethylcoualkylamine (having a number of carbon atoms within the range of 12 to 16, and having 12 in number ratio of 61%), N, N-dimethylolcoalkylamine The number of carbon atoms is in the range of 12 to 16, and the number of carbon atoms is 18 is 65%), N, N-dimethyl cured urea alkylamine And, 80%) is the ratio of the number 18, and N, N- dimethyl oleyl amine (carbon atoms in the range of 16 to 20, there may be mentioned 93%) is the ratio of the number 18.

Examples of commercially available tertiary amines represented by the general formula (17) include amines DM12D, DM14D, DM16D, DM18D, DM22D, DMCD, DMTD, DMMHTD and DMOD manufactured by Lion Corporation, have. As commercially available tertiary amines represented by the general formula (18), for example, the amines M210D, M2C, M2HT and M2O manufactured by Lion and the amino acids M2-2095 and T-08 available from Kao Corporation can be mentioned.

In this embodiment, it is preferable to use the tertiary amine represented by the general formula (18) because it is excellent in the effect of suppressing foreign matters on the coating film of the coloring composition.

[Condensation treatment]

The salt formation product (A) comprising a xanthene acid dye and an amine compound (any one selected from the group consisting of a primary amine, a secondary amine and a tertiary amine) can be synthesized by a conventionally known method.

For example, after the amine compound is dissolved in water, a xanthene acid dye is added to the aqueous solution, and the mixture is stirred. As a method for dissolving an amine compound in water, for example, it is preferable to add an amine compound together with acetic acid to water and dissolve it in water in the form of an acetate salt. The dissolved amine compound has the form of ammonium ion. (-SO ₃ H or -SO ₃ Na) in the xanthene-based acid dye and the ammonium group (NH ₄ ⁺ ) of the amine compound bond to obtain the salt formation product (A). As the solvent, methanol or ethanol may be used instead of water.

In particular, the xanthene dye C.I. The salt formation product (A) of Acid Red 289 and an amine compound having a molecular weight of 269 to 591 is excellent in solvent solubility and can achieve excellent heat resistance, light resistance and solvent resistance when used in combination with a blue pigment. The reason why good performance can be achieved when the salt formation product (A) is used in combination with the blue pigment is that the salt formation product (A) is dissolved or dispersed in the solvent and is adsorbed on the blue pigment.

(Blue pigment)

As the blue pigment, for example, a phthalocyanine-based pigment and / or a triarylmethane-based lake pigment are used in the same manner as in the first embodiment. As the phthalocyanine-based pigment, it is preferable to use a copper phthalocyanine blue pigment.

[Minification of Pigment]

The blue pigment used in the blue coloring composition of the present invention and optionally other pigments can be finely ground by a salt milling treatment as in the first embodiment. Since the primary particle diameter of the pigment is favorably dispersed in the colorant carrier, it is preferably 20 nm or more. Since the primary particle diameter of the pigment can form a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferable range is 25 to 85 nm. The primary particle diameter of the pigment is measured by a method in which the size of the primary particle is directly measured from an electron microscope photograph of the pigment by a TEM (transmission electron microscope), similarly to the first aspect.

(Other coloring agent)

As in the first embodiment, other organic pigments can be added to the blue coloring composition of the present invention as long as they do not hinder the obtaining of the effect.

The content of the pigment other than the blue pigment is preferably 20 parts by mass or less when the total mass of the coloring agent of the blue coloring composition is 100 parts by mass. If it is more than 20 parts by mass, it becomes difficult to satisfy the objective hue as blue.

<Resin>

The resin is to disperse the coloring agent, in particular the crude salt product, or to dye or penetrate the crude salt product. As the resin, for example, a thermoplastic resin or a thermosetting resin can be exemplified and used in the same manner as in the first aspect.

<Solvent>

In the blue coloring composition of the present embodiment, the coloring agent is sufficiently dispersed or dissolved in the coloring agent carrier to form a filter segment on the substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 占 퐉 Solvents may be included for ease of handling.

As the solvent, the same solvent as in the first embodiment can be used.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate (A) are preferable because of good dispersibility and solubility of the pigment and the salt formation product , Aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferably used. Among them, it is preferable to use cyclohexanone.

&Lt; Production method of colored composition >

The blue coloring composition of the present invention can be produced by mixing a coloring product (A) composed of a xanthene acid dye and an amine compound (cation component thereof), and optionally, a coloring agent such as a blue pigment, In a coloring agent carrier comprising a solvent capable of dissolving or dispersing the coloring agent. When the above material is dispersed in a colorant carrier, the blue coloring composition is preferably used in combination with a dispersing aid such as a pigment derivative or a resinous dispersant in a three-roll mill, a two-roll mill, a sand mill, a kneader, Liter or the like to a dispersion treatment using various dispersion means. The blue coloring composition of the present embodiment can also be produced by dissolving or dispersing the coloring agent (A) and other coloring agents such as a blue pigment in a colorant carrier, and then mixing them.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, as in the first aspect, a dispersion aid such as a pigment derivative, a resinous dispersant, and a surfactant can be suitably used.

In this embodiment, among the pigment derivatives, a pigment derivative represented by the following general formula (19) is preferable.

In general formula (19):

PL _m

Wherein P is an organic pigment residue, an anthraquinone residue, an acridone residue or a triazine residue, L is a phthalimidomethyl group which may have a basic substituent, an acidic substituent or a substituent, and m is an integer of 1 to 4 to be.]

Examples of the organic pigments constituting the organic pigment residue include diketopyrrolopyrrole pigments; Azo pigments such as azo, disazo and polyazo; Phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and non-metal phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone and violanthrone; Quinacridone pigments; Dioxazine pigments; Perinone pigments; Perylene pigments; Thioindigo pigments; Isoindoline pigments; Isoindolinone pigments; Quinophthalone pigments; Trene pigments; And metal complex system pigments.

In the blue coloring composition of this embodiment, the pigment derivative which is more preferably used is an amine compound of copper phthalocyanine. The amine compound of copper phthalocyanine is a basic compound (copper phthalocyanine sulfonic acid amide compound) in which P is a copper phthalocyanine residue and L is a basic substituent, P is a copper phthalocyanine residue, L is an acidic substituent, And a quaternary ammonium salt (copper phthalocyanine sulfonate ammonium salt compound), or a compound in which P is a copper phthalocyanine residue and L is a phthalimidomethyl group which may have a substituent. Among them, the pigment derivative which is most preferably used is a copper phthalocyanine sulfonic acid amide compound.

The blue coloring composition of this embodiment can also be used as a photosensitive coloring composition for a color filter by adding a photopolymerizable compound and / or a photopolymerization initiator.

&Lt; Photopolymerizable compound >

In this embodiment, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

When the filter segment is formed by the photolithography method including curing the composition by ultraviolet irradiation, the blue coloring composition for a color filter of the present invention may be prepared by adding a photopolymerization initiator or the like to a solvent- It can be prepared in the form of a development type coloring resist material.

<Increase / decrease>

The blue coloring composition for a color filter of this embodiment can further contain a sensitizer in the same manner as in the first aspect.

<Leveling agent>

To improve the leveling property of the composition on the transparent substrate, the leveling agent is preferably added to the coloring composition of the present embodiment in the same manner as in the first aspect.

<Curing agent, hardening accelerator>

The coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary in order to assist curing of the thermosetting resin, as in the first embodiment.

&Lt; Other additive components >

In the blue coloring composition of the present embodiment, a storage stabilizer may be contained in the same manner as in the first embodiment in order to keep the viscosity of the composition substantially constant over a long period of time. Further, in order to improve the adhesion with the transparent substrate, the adhesion improving agent such as a silane coupling agent may be contained in the same manner as in the first aspect.

<Antioxidant>

To increase the transmittance of the coating film, the coloring composition of the present invention preferably contains an antioxidant in the same manner as in the first aspect.

<Removal of Coarse Particles>

From the coloring composition of the present invention, it is preferable to remove coarse particles and entrained dust in the same manner as in the first aspect.

<Color filter>

The color filter of this embodiment is formed in the same manner as the first embodiment except that the blue coloring composition for a color filter of this embodiment is used.

The red filter segment can be formed using a conventional red coloring composition including a red pigment and a colorant carrier in the same manner as in the first embodiment.

In the red coloring composition, an orange color pigment and / or a yellow color pigment can be used together, as in the first aspect.

The green filter segment can be formed using a conventional green coloring composition including a green pigment and a colorant carrier in the same manner as in the first embodiment.

In the green coloring composition, a yellow pigment may be used in combination as in the first embodiment.

<Manufacturing Method of Color Filter>

The color filter of this embodiment can be produced by a printing method or a photolithography method in the same manner as in the first aspect.

(Example C)

Hereinafter, this embodiment will be described on the basis of embodiments, but the present invention is not limited thereto. Unless otherwise specified, &quot; part &quot; means &quot; part by mass &quot;. The weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation). In addition, tetrahydrofuran (THF) was used as a developing solvent.

First, an acrylic resin solution, a finely divided pigment, a salt formation product (A), a xanthene compound, a pigment dispersion, a resin solution containing a salt formation product, a resin solution containing a xanthene compound, a red resist material, The manufacturing method will be described.

&Lt; Process for producing acrylic resin solutions 1C to 4C >

(Preparation of acrylic resin solution 1C)

An acrylic resin solution 1C was prepared in the same manner as described for the alkali resin solution 1A except that cyclohexanone was used in place of propylene glycol monomethyl ether acetate (PGMAC). The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 1C was 26,000.

(Preparation of acrylic resin solution 2C)

An acrylic resin solution 2C was prepared in the same manner as described for the alkali resin solution 2A. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 2C was 18,000.

(Preparation of acrylic resin solution 3C)

An acrylic resin solution 3C was prepared by the same method as described for the alkali resin solution 3A. The weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 3C was 19,000.

(Preparation of acrylic resin solution 4C)

An acrylic resin solution 4C was obtained in the same manner as described for the alkali resin solution 4A. The weight average molecular weight (Mw) of the acrylic resin contained in this resin solution 4C was 19,000.

&Lt; Production method of micronized pigment >

(Preparation of blue fine pigment 1C)

200 parts of CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyo Ink & Chemicals, Inc., specific surface area 60 m ² / g) as a phthalocyanine blue pigment, 1400 parts of sodium chloride and 360 parts of diethylene glycol were added to a stainless steel first gallon And kneaded at 80 占 폚 for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a blue fine pigment 1C. The specific surface area of the blue fine pigment 1C was 80 m ² / g.

(Preparation of blue fine pigment 2C)

200 parts of CI Pigment Blue 1 ("Fanal Blue D 6340" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a triphenylmethane blue pigment, And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a blue fine pigment 2C. The specific surface area of the blue fine pigment 2C was 65 m ² / g.

(Preparation of purple fine pigment 1C)

200 parts of CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a purple fine pigment 1C. The specific surface area of the purple fine pigment 1C was 95 m ² / g.

(Preparation of red fine pigment 1C)

200 parts of CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Japan Co.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) as a diketopyrrolopyrrole type red pigment And kneaded at 80 DEG C for 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of red fine pigment 1C. The specific surface area of the red fine pigment 1C was 70 m ² / g.

(Preparation of yellow fine pigment 1C)

, 500 parts of CI Pigment Yellow 139 ("Irgafour Yellow 2R-CF" manufactured by Chiba Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were mixed with a stainless steel first gallon kneader ), And kneaded at 120 DEG C for 8 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to obtain 490 parts of yellow fine pigment 1C. The specific surface area of the yellow fine pigment 1C was 70 m ² / g.

(Preparation of Green Fine Pigment 1C)

200 parts of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel first gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) And kneaded at 80 DEG C over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of a green fine pigment 1C. The specific surface area of the green fine pigment 1C was 75 m ² / g.

(Preparation of yellow fine pigment 2C)

200 parts of CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho Co., Ltd.) Over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 85 ° C to obtain 190 parts of yellow fine pigment 2C. The specific surface area of the yellow fine pigment 2C was 65 m ² / g.

&Lt; Preparation method of salt formation product (A) >

(Preparation salt product (A-1C))

By the following procedure, C.I. (A-1C) comprising Acid Red 289 and stearylamine (Kao Gemamine 80) (molecular weight of 269) was prepared.

Stearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-1C) as a product salt product of Acid Red 289 and stearylamine.

(Preparation salt product (A-2C))

By the following procedure, C.I. (A-2C) comprising Acid Red 289 and distearylamine (Kao Zephamine D80) (molecular weight: 521) was prepared.

Distearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-2C) as a product salt product of Acid Red 289 and distearylamine was obtained.

(Preparation salt product (A-3C))

By the following procedure, C.I. (A-3C) comprising Acid Red 289 and a dicocoalkylamine (molecular weight of 353) was prepared.

Diccoalkylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-3C) as a product salt product of Acid Red 289 and dicocoalkylamine.

(Preparation salt product (A-4C))

By the following procedure, C.I. (A-4C) comprising Acid Red 289 and N-methyldodecylamine (molecular weight: 311) was prepared.

N-methyldodecylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-4C) as a product salt product of Acid Red 289 and N-methyldodecylamine.

(Preparation salt product (A-5C))

By the following procedure, C.I. (A-5C) comprising Acid Red 289 and N-methyldi-cured Uji alkylmethylamine (molecular weight in the range of 367 to 591) was prepared.

N-methyldi-cured urea alkylmethylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-5C) as a product salt product of Acid Red 289 and N-methyldi-cured urea alkylmethylamine was obtained.

(Preparation salt product (A-6C))

By the following procedure, C.I. (A-6C) comprising Acid Red 289 and N-butyldimethylamine (molecular weight: 101) was prepared.

N-butyldimethylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-6C) as a product salt product of Acid Red 289 and N-butyldimethylamine.

(Preparation salt product (A-7C))

By the following procedure, C.I. (A-7C) comprising Acid Red 52 and distearylamine (Kao Zephamine D80) (molecular weight: 521) was prepared.

Distearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 52 was added dropwise little by little. C.I. Acid red 52 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-7C) which is a product salt product of Acid Red 52 and distearylamine.

(Preparation salt product (A-8C))

By the following procedure, C.I. (A-8C) comprising Acid Red 87 and Distearylamine (Kao Zephamine D80) (molecular weight: 521) was prepared.

Distearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 87 was added dropwise little by little. C.I. Acid red 87 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-8C) which is a product salt product of Acid Red 87 and distearylamine.

(Preparation salt product (A-9C))

By the following procedure, C.I. (A-9C) comprising Acid Red 92 and Distearylamine (Kao Zephamine D80) (molecular weight: 521) was prepared.

Distearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 92 was added dropwise little by little. C.I. Acid Red 92 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-9C) as a product salt product of Acid Red 92 and distearylamine.

(Salt formation product (A-10C))

By the following procedure, C.I. (A-10C) comprising Acid Red 388 and distearylamine (Kao Zephamine D80) (molecular weight: 521) was prepared.

Distearylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 388 was added dropwise little by little. C.I. Acid red 388 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-10C) as a product salt product of Acid Red 388 and distearylamine.

(Salt formation product (A-11C))

By the following procedure, C.I. (A-11C) comprising Acid Red 289 and dipropylamine (Tokyo Chemical Industry Co., Ltd.) (molecular weight: 101) was prepared.

Dipropylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was sufficiently stirred. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-11C) as a product salt of the salt of the acid red 289 and dipropylamine.

(Preparation salt product (A-12C))

By the following procedure, C.I. (A-12C) comprising Acid Red 289 and dibeenylmethylamine (molecular weight: 647) was prepared.

Dibehenylmethylamine was added to an aqueous solution of 10 to 20% of acetic acid, and this solution was stirred for 10 minutes. After this solution was heated to 60 캜, C.I. Acid Red 289 was added dropwise little by little. C.I. Acid red 289 may be used as an aqueous solution. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-12C) as a product salt product of Acid Red 289 and dibeenylmethylamine.

&Lt; Method for producing xanthan family compound >

(Xanthene compounds (C-1C) and (C-2C))

(C-1C) and (C-2C) were prepared in the same manner as described above for the xanthene compounds (C-1A) and (C-2A).

&Lt; Production method of pigment dispersion >

(Production of pigment dispersion (DP-1C)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a pigment dispersion (DP-1C).

Blue Fine Pigment 1C (CI Pigment Blue 15: 6): 9.5 parts

Dye derivative 1C (copper phthalocyanine sulfonic acid amide compound): 1.5 parts

Surfactant 1C (Toray N-120 (palm oil fatty acid monoethanolamide) manufactured by Tohoku Kagaku): 0.2 part

Acrylic resin solution 1C: 39.8 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Chiba Japan): 1.0 part

The dye derivative 1C (copper phthalocyanine sulfonic acid amide compound) is a mixture containing m = 1 of the compounds represented by the following structural formulas and m = 2 of the compounds represented by the following structural formulas in a mass ratio of 65:35.

(Production of pigment dispersion (DP-2C)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a pigment dispersion (DP-2C).

Blue Fine Pigment 2C (CI Pigment Blue 1): 11.0 parts

Acrylic resin solution 1C: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Chiba Japan): 1.0 part

(Preparation of Pigment Dispersions (DP-3C) to (DP-7C)) [

Pigment dispersions (DP-3C) to (DP-7C) were prepared in the same manner as the pigment dispersion (DP-2C) except that the blue fine pigment 1C was changed to the pigment shown in Table 13.

&Lt; Preparation method of a resin solution containing a salt formation product and a resin solution containing a xanthene compound >

(Preparation of a salt solution-containing resin solution (DA-1C)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a resin solution (DA-1C) containing the salt formation product.

Preparation salt product (A-1C): 11.0 parts

Acrylic resin solution 1C: 40.0 parts

Cyclohexanone: 49.0 parts

(Preparation of Decomposition Product-Containing Resin Solution (DA-2C) to (DA-12C) and Xanthene Compound-Containing Resin Solution (DC-1C) and (DC-2C)

Containing resin solution (DA-1C) was obtained in the same manner as in the above-described formation product containing resin solution (DA-1C) except that the crude product (A-1C) (DA-2C) to (DA-12C) and a xanthene-based compound-containing resin solution (DC-1C) and (DC-2C) were prepared.

&Lt; Preparation method of red and green resist material >

(Preparation of red resist material)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain a red resist material.

Pigment dispersion (DP-4C): 50.0 parts

Pigment dispersion (DP-5C): 10.0 parts

Acrylic resin solution 1C: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.: 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Preparation of green resist material)

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain a green resist material.

Pigment dispersion (DP-6C): 45.0 parts

Pigment dispersion (DP-7C): 15.0 parts

Acrylic resin solution 1C: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 1C to 12C and Comparative Examples 1C and 2C]

(Example 1C: Coloring composition (DB-1C))

The following mixture was stirred so as to be homogeneous, and then filtered with a 5.0 占 퐉 filter to obtain a mixed colored composition.

Salt solution containing resin solution (DA-1C): 2.2 parts

Pigment dispersion (DP-1C): 8.8 parts

Acrylic resin solution 1C: 40.0 parts

Cyclohexanone: 49.0 parts

(Examples 2C to 12C and Comparative Examples 1C and 2C: Coloring compositions (DB-2C) to (DB-14C))

Except that the coloring composition (DB-1C) was used in the same manner as the coloring composition (DB-1C) except that the salt solution containing resin solution (DA-1C) -2C) to (DB-14C) were prepared.

(Method of foreign matter test on coated film)

The above coloring composition was evaluated for ease of occurrence of coating irregularity due to foreign matter. Specifically, first, the coloring composition was applied on a transparent substrate so that the dry film thickness was about 2.0 占 퐉, and this was heated in an oven at 230 占 폚 for 20 minutes to obtain a test substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five visual fields, the number of observable particles was counted, and the total number of particles was obtained. Table 15 shows the results.

In Table 15, the meanings of the symbols described in the column of &quot; foreign matter on the coating film &quot; are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

When the total number of particles is less than 20, coating irregularities caused by foreign matters hardly occur. When the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. When the total number of particles is 100 or more, coating unevenness (smudge) due to foreign matter occurs.

The coating film obtained from the coloring composition containing the salt formation product (A) and the blue pigment of the present invention had few foreign matters (unidentified foreign matters). On the other hand, the coating film obtained from the coloring composition containing the xanthene-based compounds (C-1C) and (C-2C) had a very large number of foreign substances. That is, when a xanthene dye is bathed with a primary, secondary or tertiary amine, excellent performance can be achieved as compared with the case where a functional group of a xanthene dye is substituted.

In Examples 6C and 11C, the molecular weight of the cationic portion of the crude salt product was 101, which was small compared to Examples 1C to 10C. Therefore, in Examples 6C and 11C, there were many foreign matters on the coating film as compared with Examples 1C to 10C. However, the amounts of coating foreign matters in Examples 6C and 11C satisfied practical levels.

In Example 1C, the crude product of the primary amine and the xanthene dye was used. In Examples 2C and 3C, the crude product of the secondary amine and the xanthene dye was used. In Examples 4C to 6C, the tertiary amine and the xanthene- The salt-forming product with the dye was used. Since all of these amines contained an alkyl chain having 8 or more carbon atoms, in Examples 1C to 6C, evaluation results on foreign matters on the coating film were satisfactory. Particularly, in the case of the secondary amine, excellent results were obtained as compared with the case of the primary amine, and in the case of the tertiary amine, more excellent results were obtained.

[Examples 13C to 32C and Comparative Examples 3C to 5C]

(Example 13C: Resist material (R-1C)) [

The following mixture was stirred so as to be homogeneous, and then filtered with a filter of 1.0 mu m to obtain an alkali development type resist material (R-1C).

Salt solution containing resin solution (DA-1C): 12.0 parts

Pigment dispersion (DP-1C): 48.0 parts

Acrylic resin solution 1C: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Cyclohexanone: 23.2 parts

(Examples 14C to 32C and Comparative Examples 3C to 5C: Resist materials (R-2C) to (R-23C)

Except that the type and amount of the colorant-containing resin solution and the pigment dispersion and the kind of the acrylic resin solution were changed as shown in Table 16, the same procedure as in the case of the resist material (R-1C) -2C) to (R-23C).

(Evaluation of resist material)

Coatings were formed from the resist materials (R-1C) to (R-23C), and chromaticity, foreign matter amount, heat resistance, light resistance and solvent resistance were examined for each of these coating films by the following methods. Table 17 shows the results of the test.

(Foreign Film Test)

The above resist material was evaluated for ease of occurrence of coating irregularity caused by foreign matter. Specifically, first, a resist material was applied on a transparent substrate so that the dry film thickness was about 2.5 占 퐉, and the entire surface of the coated film was exposed with ultraviolet rays. Thereafter, this was heated in an oven at 230 DEG C for 20 minutes and then cooled to obtain an evaluation substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five fields of view, the number of identifiable particles was counted and the total number of particles was requested. The results are shown in Table 17.

In Table 17, the meanings of the symbols described in the column of "foreign matter on the coating film" are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

(Evaluation of color characteristics)

A resist material was applied on the glass substrate. Specifically, the above resist material was coated with a film thickness such that the chromaticity under the C light source was x = 0.150, y = 0.060. These substrates were heated at 230 占 폚 for 20 minutes to form colored layers on the substrates. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Table 17 shows the results.

(Coating film heat resistance test)

The resist material was coated on the transparent substrate so that the dry film thickness became about 2.5 占 퐉, and the coating film was exposed to ultraviolet rays through a mask having a predetermined pattern. This coating film was sprayed with an alkali developing solution to remove the uncured portions to form a desired pattern. This was then heated in an oven at 230 占 폚 for 20 minutes. After cooling down, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film under a C light source was measured using a brown spectrophotometer (OSP-SP200 manufactured by Olympus Kogaku Co., Ltd.) . Thereafter, this was provided to a heat resistance test in which the plate was heated in an oven at 250 DEG C for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured.

Using these chromaticity values, the color difference? Eab * was calculated by the following calculation formula. Then, based on the color difference ([Delta] Eab *), the heat resistance of the coating film was evaluated by the following five steps.

&Amp; cir &amp;: DELTA Eab * is less than 0.5

?:? Eab * is not less than 0.5 and less than 1.5

○: ΔEab * is not less than 1.5 and less than 2.5

DELTA: Eab * is not less than 2.5 and less than 5.0

X:? Eab * was 5.0 or more

The results are shown in Table 17.

(Coating light resistance test)

(1), a * (1) and b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.) Quot;). Thereafter, the substrate was placed in a light resistance tester (&quot; SUNTEST CPS + &quot; manufactured by TOYOSEIKI), and left for 500 hours. After removal of the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these chromaticities, the color difference (ΔEab *) was calculated in the same manner as in the coating film heat resistance test, and the light resistance of the coating film was evaluated based on the same criteria as the heat resistance. Table 17 shows the results.

(Test for solvent resistance of coating film)

(L * (1), a * (1), b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., ). Subsequently, the substrate was immersed in N-methylpyrrolidone for 30 minutes. (2) (L * (2), a * (2), b * (2)) under a C light source were measured after removal of the substrate. Using these chromaticity diagrams, ), And the solvent resistance of the coating film was evaluated based on the same criteria as the heat resistance. Table 17 shows the results.

The coloring layer obtained from the blue coloring composition for a color filter containing the xanthate acidic dye and the salt formation product (A) comprising the primary, secondary or tertiary amine and the blue pigment is excellent in lightness and resistance, Excellent results were obtained.

Since the resist materials (R-13C) and (R-18C) contained dioxazine violet pigment, the lightness of the coloring layer obtained from the resist materials R-13C and (R-18C) was slightly low, . The colored layers obtained from the resist materials (R-13C) and (R-18C) were particularly excellent in heat resistance, light resistance and solvent resistance.

The colored layers obtained from the resist materials (R-14C) and (R-19C) were excellent in color characteristics. The coloring layers obtained from the resist materials (R-14C) and (R-19C) were slightly low in heat resistance, light resistance and solvent resistance, but were of no problem for use in color filters.

Resist materials (R-6C) and (R-11C) contained a salt formation product of an amine compound having a molecular weight of 101 and a xanthene dye. On the other hand, since the resist material (R-12C) contained a salt formation product of an amine compound having a molecular weight of 647 and a xanthene dye, the coloring layer obtained from the resist material (R-12C) had a slightly lower transmittance and therefore a slightly lower brightness. However, all of them satisfied the practical level.

On the other hand, the colored layers obtained from the resist materials (R-21C) and (R-22C) had many foreign matters. The coloring layer obtained from the resist material (R-23C) had a lower brightness Y than the coloring layer obtained from the resist materials (R-1C) to (R-20C).

As can be seen from the results obtained for the resist materials (R-15C) to (R-17C) and (R-20C), the use of the active energy ray- The solvent resistance is improved.

[Examples 33C to 52C and Comparative Example 6C]

(Example 31C: Color filter (CF-1C)) [

A black matrix as a light shielding pattern was formed on a glass substrate, and then a red resist material was applied using a spin coater. The red resist material was applied in such a thickness that the chromaticity under the C light source was x = 0.640, y = 0.330. This coating film was irradiated with ultraviolet rays at an exposure dose of 300 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was subjected to a spraying development using an alkali developing solution composed of an aqueous solution of sodium carbonate of 0.2 mass% to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was further heated at 230 DEG C for 20 minutes to form a red filter segment.

Next, a green resist material was applied onto the substrate by the same method as described above. The green resist material was applied in such a thickness that the chromaticity under the C light source was x = 0.300 and y = 0.600. This coating film was subjected to the same exposure, development, cleaning, and firing as described above with respect to the red filter segment to form a green filter segment.

On this substrate, a blue resist material (R-1A) was applied by the same method as described above. The blue resist material (R-1A) was applied in such a thickness that the chromaticity under the C light source was x = 0.150 and y = 0.060. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a blue filter segment. Thus, a color filter CF-1C was obtained.

(Production of liquid crystal display)

An electrode made of ITO was formed on the color filter (CF-1C), and a polyimide alignment layer was formed thereon. In addition, a TFT array and a pixel electrode were formed on one surface of a glass substrate prepared separately, and an orientation layer made of polyimide was formed thereon.

Next, on the surface of the one glass substrate on which the electrodes were provided, a rim-shaped pattern having a passage communicating between the inside and the outside of the rim was formed using a sealant. Subsequently, these substrates were stuck together with the spacer beads interposed therebetween such that the electrodes faced each other.

Subsequently, the liquid crystal composition was injected into the internal space of the thus obtained cell from the above passage. After sealing the passageway, a polarizing plate was attached to both sides of the cell to obtain a liquid crystal display panel.

Thereafter, a liquid crystal display was completed by combining a liquid crystal display panel and a backlight unit including three-wavelength CCFL.

(Examples 34C to 52C and Comparative Example 6C)

(CF-2C) to (CF-21C) and a liquid crystal display in the same manner as the color filter (CF-1C) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 18 . In addition, since the coloring layers obtained from the blue resist materials (R-21C) and (R-22C) had very many foreign matters on the coating film, the production of color filters using them was not carried out.

(Evaluation of color filters (CF-1C) to (CF-21C)

The color image was displayed on the liquid crystal display, and the brightness of the area corresponding to the red, green, and blue filter segments was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Then, the brightness of the white display was obtained from these brightness values. The results are shown in Table 18.

The blue coloring layers of the color filters (CF-1C) to (CF-20C) are formed of a resist material containing the blue pigment and the salt formation product (A). On the other hand, the blue coloring layer of the color filter (CF-21C) is formed from a resist material containing a copper phthalocyanine pigment and a dioxazine-based pigment. As shown in Table 18, the liquid crystal display including the color filters (CF-1C) to (CF-20C) can display a white image with a higher brightness compared with the liquid crystal display including the color filter .

○ The fourth sun

Next, the fourth aspect will be described.

The blue coloring composition for a color filter according to the fourth aspect contains a binder resin and a coloring agent. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed of a compound having a cationic group and a xanthene acid dye. In this embodiment, as the compound having a cationic group, a resin having a cationic group in the side chain is used.

When the blue coloring composition according to the fourth aspect is used in the production of a color filter, it becomes possible to realize a high brightness and a wide color reproduction area. Further, since the dye is in the form of a salt formation product, the heat resistance, light resistance and solvent resistance Excellent performance can be achieved.

In addition, the transmission spectrum of a blue coloring composition for a color filter in which a conventional copper phthalocyanine blue pigment and a dioxazine-based pigment are combined has a peak position near 450 nm, and a transmittance sharply decreases on a short wavelength side of 450 nm or shorter.

On the other hand, when the blue coloring composition for a color filter according to the present embodiment is used, a high transmittance is achieved at a short wavelength side of 450 nm or less as compared with the case of using a combination of a copper phthalocyanine blue pigment and a dioxazine pigment. Incidentally, the emission spectrum of many backlights such as cold-cathode tubes has a peak wavelength in or near the wavelength range of, for example, 425 to 500 nm. Therefore, the filter segment obtained from the blue coloring composition for a color filter according to the present embodiment can achieve high brightness.

<Preparation salt product (A)>

(A resin having a cationic group in the side chain)

The resin having a cationic group in the side chain for obtaining the salt formation product (A) used in this embodiment will be described. This resin is not particularly limited as long as it has at least one onium base in its side chain. The onium salt structure is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt or a phosphonium salt from the viewpoint of availability and the like. From the viewpoint of storage stability (thermal stability), ammonium salts, iodonium salts or sulfonium salts . More preferably, it is an ammonium salt.

When a blue coloring composition for a color filter containing the salt formation product (A) is prepared and the characteristics as a color filter are expressed, it is preferable to use a resin similar to the binder resin constituting the blue coloring composition for a color filter. In this embodiment, an acrylic resin is preferably used as the binder resin of the coloring composition for a color filter, and therefore it is preferable that the resin having a cationic group in the side chain for obtaining the salt formation product (A) is an acrylic resin.

As the resin having a cationic group in the side chain of the present embodiment, an acrylic resin containing a structural unit represented by the following general formula (20) can be used.

The general formula (20)

[In the general formula (20), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, wherein _{two of} R ₂ to R ₄ are bonded to each other to form a ring . Q represents an alkylene group, an arylene _{group, -CONH-R 5 -, -COO} -R 5 - represents a, R ₅ represents an alkylene group. Y ^- represents an inorganic or organic anion.]

In the general formula (20), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. The alkyl group for R ₁ includes, for example, methyl, ethyl, propyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among them, R ₁ is most preferably a hydrogen atom or a methyl group.

In the general formula (20), R ₂ to R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

Examples of the alkyl group in R ₂ to R ₄ include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, N-hexadecyl and n-octadecyl), branched alkyl groups (such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert- (Such as norbornyl, adamantyl, and pyranyl) and cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl) and crosslinked cyclic alkyl groups . The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl group in R ₂ to R ₄ include linear or branched alkenyl groups such as vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, Methyl-1-propenyl, 2-methyl-2-propenyl, etc.) and cycloalkenyl groups (2-cyclohexenyl and 3-methyl- -Cyclohexenyl and the like). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R ₂ to R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphtho (Group derived from pyridine), pyridyl (group derived from pyran), pyridyl (group derived from pyridine), aromatic heterocyclic hydrocarbon group (thienyl , 9-oxoxanthanyl (a group derived from xanthone), and 9-oxothioxanethenyl (a group derived from a thioxanthone)).

When the alkyl group, alkenyl group or aryl group represented by R ₂ to R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxyl group, an alkenyl group, an acyl group, an alkoxycarbonyl group, And a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group and a phenyl group are particularly preferable.

As R ₂ to R _4, an alkyl group which may be substituted from the viewpoint of stability is preferable, and an unsubstituted alkyl group is more preferable.

_{Two of} R ₂ to R _{4 may} be bonded to each other to form a ring.

In the general formula (20), the component of Q connecting the acrylic moiety and the ammonium salt group represents an alkylene group, an arylene group, -CONH-R ₅ -, -COO-R ₅ -, and R ₅ represents an alkylene group. Among them, -CONH-R ₅ - and -COO-R ₅ - are preferable because of their ease of polymerization and availability. It is more preferable that R ₅ is a methylene group, an ethylene group, a propylene group or a butylene group, and an ethylene group is particularly preferable.

The component Y ^- in the general formula (20) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, any known one can be used without limitation, and specifically, a hydroxide ion; Halogen ions such as chloride ion, bromide ion and iodide ion; Carboxylic acid ions such as formic acid ion and acetic acid ion; A complex ion such as a carbonate ion, a bicarbonate ion, a nitrate ion, a sulfate ion, a sulfite ion, a chromate ion, a dichromate ion, a phosphate ion, a cyanide ion, a permanganate ion and a hexacyano iron (III) . In terms of synthetic suitability and stability, halogen ions and carboxylic acid ions are preferred, and halogen ions are most preferred. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded to the resin to form a salt in the molecule.

The acrylic resin containing the structural unit represented by the general formula (20), which is a preferred embodiment of the present invention, can be obtained by, for example, copolymerizing an ethylenically unsaturated monomer having an ammonium salt group as a monomer component. Alternatively, the acrylic resin may be obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component to obtain an acrylic resin having an amino group, and then reacting with an onium chloride to form an ammonium salt do.

Specific examples of the ethylenically unsaturated monomers usable for obtaining the acrylic resin containing the structural unit represented by the general formula (20) are shown below.

Examples of the ethylenic unsaturated monomer having a quaternary ammonium salt group include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzyl Alkyl (meth) acrylate quaternary ammonium compounds such as ammonium chloride, and (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyl Alkyl (meth) acryloylamide type quaternary ammonium compounds such as aminoethyltriethylammonium chloride and (meth) acryloylaminoethyldimethylbenzylammonium chloride, dimethyldiallylammonium methylsulfate, and trimethylvinylphenylammonium chloride .

Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (Meth) acrylate, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, ditbutylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (Meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (Meth) acrylic acid esters or (meth) acrylamides having a dialkylamino group such as butylaminopropyl (meth) acrylamide; Styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; Diallylamine compounds such as diallylmethylamine and diallylamine; And amino group-containing aromatic vinyl-based monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

Examples of the onium chlorinating agent include alkylsulfuric acids such as dimethylsulfuric acid, diethylsulfuric acid and dipropylsulfuric acid, sulfonic acid esters such as methyl p-toluenesulfonate and methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride and octyl chloride Alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide and octyl chlorobromide, and benzyl chloride and benzyl bromide.

The reaction of the ethylenically unsaturated monomer having an amino group with the onium chloride can be carried out by dropping an onium chloride agent having an equimolar amount or less with respect to the amino group into an ethylenically unsaturated monomer solution having an amino group. The temperature at the time of the ammonium chloride conversion is about 90 ° C or lower, particularly preferably about 30 ° C or lower when the vinyl monomer is converted into ammonium chloride, and the reaction time is about 1 to 4 hours.

As the onium chloride, alkoxycarbonylalkyl halide may be used. The alkoxycarbonylalkyl halide is represented by the following general formula (21).

In general formula (21):

ZR ₆ -COOR ₇

[In the formula (21), Z is a halogen such as chlorine and bromine, preferably bromine, and R ₆ is an alkylene group having 1 to 6, preferably 1 to 5, more preferably 1 to 3 carbon atoms And R &lt; ₇ &gt; is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

The reaction of an ethylenically unsaturated monomer having an amino group with an alkoxycarbonylalkyl halide can be carried out by reacting an alkoxycarbonylalkyl halide having an equimolar molarity with respect to an amino group in the same manner as in the case of the onium chlorinating agent and then hydrolyzing -COOR ₇ , ion (-COO ^-), by conversion to be obtained. As a result, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (21) and having an ammonium salt group can be obtained.

Examples of other ethylenically unsaturated monomers that can be used in addition to the structural unit represented by formula (20) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters (Meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such vinyl monomers include, for example, the following compounds.

Examples of the (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl Acrylate such as 2-ethoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl Ethylene glycol monomethyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid trie (Meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate,? -Phenoxyethoxyethyl (Meth) acrylic acid nonylphenoxypolyethylene glycol, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (Meth) acrylate, perfluorooctylethyl acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylate, and (meth) acrylamidopropyltrimethoxysilane.

Examples of the crotonic acid esters include butyl crotonate and hexyl crotonate.

Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate.

Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, dibutyl itaconate and the like.

Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (Meth) acrylamide, N, N-butyl (meth) acrylamide, N-cyclohexyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, .

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

Examples of the styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene , Chloromethylstyrene, hydroxystyrene protected with a group capable of being deprotected by an acidic substance (e.g., t-Boc), methyl vinylbenzoate, and? -Methylstyrene.

Other ethylenically unsaturated monomers that can be used in addition to the structural unit represented by the general formula (20) may further include a copolymerization unit derived from a monomer having an acid group.

Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, and cinnamic acid; Unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; An unsaturated polycarboxylic acid having three valencies or more or anhydrides thereof; (2-acryloyloxyethyl) succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl) Mono [(meth) acryloyloxyalkyl] esters of a divalent or higher polyvalent carboxylic acid, for example, mono (meth) acrylates of both terminal carboxy polymers such as? -carboxy-polytone caprolactone monoacrylate and? -carboxy-polycaprolactone monomethacrylate.

As a method of obtaining the acrylic resin containing the structural unit represented by the general formula (20), known methods such as anion polymerization, living anion polymerization, cation polymerization, living cation polymerization, free radical polymerization, and living radical polymerization can be used . Of these, free radical polymerization or living radical polymerization is preferred.

In the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound or an organic peroxide can be used. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile) Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis Azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2-methylpropionate], and 2,2'-azobis 2- (2-imidazolin-2-yl) propane]. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propylperoxydicarbonate, di (2- ethoxyethyl) peroxydicarbonate, Peroxyneodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide. These polymerization initiators may be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 占 폚, more preferably 50 to 110 占 폚. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

In the living radical polymerization method, side reactions occurring in general radical polymerization are suppressed, and the polymerization is uniformly grown. Therefore, a block polymer or a resin having a constant molecular weight can be easily synthesized.

Among them, the atom transfer radical polymerization method using an organohalide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst can adopt a wide range of monomers and can adopt a polymerization temperature applicable to existing equipment . The atom transfer radical polymerization can be carried out by the methods described in References 1 to 8 below.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329

(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921

(Reference 3) Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614

(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866

(Reference 5) WO96 / 030421

(Reference 6) WO97 / 018247

(Reference 7) Japanese Patent Application Laid-Open No. 9-208616

(Reference 8) Japanese Patent Application Laid-Open No. 8-41117

It is preferable to use an organic solvent for the polymerization. Examples of the organic solvent include, but are not limited to, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, Propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate is used. These solvents may be used in a mixture of two or more kinds.

The amount of the cationic group present in the resin having a cationic group in the side chain is not particularly limited, but it is preferably 10 to 200 mgKOH / g and more preferably 20 to 130 mgKOH / g. The lowering of the cation is represented by an onium salt, a quaternary ammonium salt, and an amine salt. The amount of the ammonium salt group and the amine base in the acrylic resin containing the structural unit represented by the general formula (20) is preferably from 10 to 200 mgKOH / g, more preferably from 20 to 130 mgKOH / g, desirable.

If it is smaller than 10 mgKOH / g, the concentration of the dye derived from the xanthene acid dye is low and the resin component becomes large, so that it can not function as a colorant component. Further, if it exceeds 200 mgKOH / g, the dye component becomes large and solvent solubility is lowered.

The molecular weight of the acrylic resin containing the structural unit represented by the general formula (20) is not particularly limited. The converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 3,000 to 15,000.

The acrylic resin containing the structural unit represented by the general formula (20) is preferably soluble in a solvent widely used in a coloring composition for a color filter. As a result, a coating film free from foreign substances can be obtained. Particularly, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (20) is not particularly limited, but when the total structural unit contained in the resin having a cationic group in the side chain is 100 parts by mass , The total content of the structural units represented by the general formula (20) is preferably 5 parts by mass or more, and more preferably 10 to 50 parts by mass in view of the solvent solubility and tinting power of the salt formation product.

(Xanthene acid dye)

The xanthene-based acid dye for obtaining the salt formation product (A) can be used in the same manner as in the first embodiment.

(Salt formation)

The starting salt product (A) used in the present invention is obtained by stirring or vortexing an aqueous solution in which a resin having a cationic group and a xanthene acid dye are dissolved in the side chain, or by mixing an aqueous solution of a resin having a cationic group in the side chain and a xanthene acid dye Can be easily obtained by mixing an aqueous solution of the compound In the aqueous solution, the cationic group of the resin and the anionic group of the xanthene acidic dye are ionized, and they are ionized and the ion-bonded portion becomes water-insoluble, causing precipitation. On the other hand, the salt composed of the counter anion of the resin and the relative cation of the xanthene acid dye is water-soluble and can be removed by washing with water or the like. As each of the resin having a cationic group in the side chain and the xanthene acid dye, only one kind may be used, or a plurality of types having different structures may be used.

In the salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin having a cationic group and the xanthene acid dye in the side chain. Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1- Ethoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, diethylene glycol monomethyl ether, Triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, (2-pyrrolidone, 2-methylpyrrolidone, N-methylpyrrolidone, N-methylpyrrolidone, N, N-dimethylformamide, 2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, tetrafurfuryl alcohol, and 4-methoxy-4 methylpentanone. These water-soluble organic solvents are preferably used in an amount of 5 to 50 parts by mass, and most preferably 5 to 20 parts by mass, when the total mass of the aqueous solution is 100 parts by mass.

The content of the dye component derived from the xanthine acid dye in the salt formation product (A) can be controlled within a range of 10 to 60 parts by mass, particularly preferably within a range of 15 to 55 parts by mass, relative to 100 parts by mass of the product (A) . Controlled in this range, it is possible to obtain a salt formation product (A) having excellent solvent solubility.

The amount of the effective dye component (excluding the counter ion such as alkali metal ion) in the xanthate acid dye contained in the salt formation product (A) is preferably the same as that of the salt product (A) solution and the xanthene acid dye solution The spectrum can be measured and the spectral intensity ratio of the maximum absorption wavelength can be calculated.

For example, a solution of the salt formation product (A) and a solution of a xanthene acid dye (A) and a xanthene acid dye (B) are prepared by using a solvent capable of dissolving both the salt formation product And the absorbance at the maximum absorption wavelength of the salt solution (A) solution and the xanthine acid dye solution obtained by absorbance measurement are Xa and Xb, respectively. The xanthene acid dye generally contains counter ions such as alkali metal ions. In this case, the number of counter ions present in one molecule is Na, the atomic weight of the counter ion is Ma, the molecular weight of the xanthene acid dye Is Mb, the mass% of the effective dye component in the xanthene acid dye is given by the following formula.

(1-Ma x Na / Mb) x 100 [mass%]

Using this formula, the mass% of the effective dye component in the xanthate acid dye contained in the salt formation product (A) can be calculated from the following formula.

(Xa / Xb) x (1-Ma x Na / Mb) x 100 [mass%]

(Blue pigment)

As the blue pigment constituting the colorant used in this embodiment, a phthalocyanine-based pigment and / or a triarylmethane-based lake pigment or the like is used in the same manner as in the first embodiment. As the phthalocyanine-based pigment, it is preferable to use a copper phthalocyanine blue pigment.

Among these, C.I. pigment is preferred as a blue pigment since it has excellent heat resistance and coloring property. Pigment Blue 15: 6, C.I. Pigment Blue 1 is preferably used.

[Minification of Pigment]

The blue pigment to be used in the blue coloring composition of the present invention, and the optionally usable pigment, can be finely ground by a salt milling treatment in the same manner as in the second aspect.

The primary particle diameter of the pigment can be obtained by a method in which the size of the primary particle is directly measured from an electron microscope photograph of the pigment photographed using a TEM (transmission electron microscope) in the same manner as in the second aspect.

The salt formation product (A) is preferably used in an amount of 1 to 800 parts by mass with respect to 100 parts by mass of the blue pigment. The amount of the salt formation product (A) is more preferably 5 to 400 parts by mass. If the addition amount of the salt formation product (A) is less than 1 part by mass, the reproducible chromaticity region is narrowed, and if it exceeds 800 parts by mass, the color is changed.

It is preferable that the effective dye component of the xanthate acid dye in the salt formation product (A) is 1 to 400 parts by mass relative to 100 parts by mass of the blue pigment. The effective dye component of the dye is more preferably in the range of 5 to 300 parts by mass with respect to 100 parts by mass of the blue pigment.

The salt formation product (A) is preferably a C.I. Acid Red 289 or C.I. In the case of using the Acid Red 52, excellent solvent solubility is exhibited and excellent heat resistance, light resistance and solvent resistance are achieved when used in combination with a blue pigment.

The reason why the salt formation product (A) is used in combination with the blue pigment to achieve good performance is because the salt formation product is adsorbed on the blue pigment while dissolving or dispersing in the solvent.

(Other coloring agent)

In the blue coloring composition of this embodiment, in addition to the components of the coloring agent, other organic pigments may be added to the blue coloring composition as long as the effect is not adversely affected, as in the first embodiment.

<Binder Resin>

The binder resin is to disperse the coloring agent, especially the salt-forming product, or to dye or penetrate the salt-forming product. As the binder resin, there can be mentioned a thermoplastic resin and a thermosetting resin, and they can be used in the same manner as the &quot; resin &quot; in the first aspect.

<Organic solvents>

The blue coloring composition of this embodiment can contain an organic solvent in the same manner as in the first embodiment.

Of these, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like, which are excellent in dispersion and dissolution of the pigment and salt formation product (A) It is preferable to use aromatic alcohols such as glycol acetates and benzyl alcohol, or ketones such as cyclohexanone. Particularly, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety hygiene and low viscosity.

These organic solvents may be used singly or in combination of two or more kinds. When two or more mixed solvents are used, it is preferable that the ratio of the above-mentioned preferable organic solvent to the total organic solvent (100% by mass) is 65 to 95% by mass. Particularly, it is preferable that propylene glycol monomethyl ether acetate is the main component, and it is preferable that the ratio of the propylene glycol monomethyl ether acetate to the total organic solvent is 65 to 100 mass%.

The organic solvent is preferably used in an amount of 800 to 4000 parts by mass when the total mass of the coloring agent is 100 parts by mass from the viewpoint of forming the desired filter layer with a desired film thickness by controlling the coloring composition to an appropriate viscosity Do.

<Dispersion>

The blue coloring composition is obtained by mixing a blue pigment and a salt formation product, in this case, a coloring agent containing the salt formation product (A) obtained by reacting a resin having a cationic group in a side chain with a xanthate acid dye, with a binder resin and a solvent To a treatment using various dispersion means such as 3 roll mill, 2 roll mill, sand mill, kneader, and stirrer, together with a dispersion aid such as a pigment derivative, preferably in a colorant carrier comprising The blue coloring composition can also be produced by dispersing the blue pigment, the salt formation product (A) and other coloring agents in the respective colorant carriers, and then mixing them.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, a dispersion aid such as a pigment derivative, a resinous dispersant, and a surfactant may be suitably used.

In the case of the blue coloring composition of this embodiment, it is preferable to use a basic compound of copper phthalocyanine, in which a basic substituent group is introduced into the phthalocyanine pigment, in the same manner as in the second embodiment as the pigment derivative. The basic compound of copper phthalocyanine is preferably an amine compound of copper phthalocyanine, and examples thereof include copper phthalocyanine sulfonate ammonium salt compound, copper phthalocyanine tertiary amine, and copper phthalocyanine sulfonate amide compound.

In the blue coloring composition of the present embodiment, the mass ratio (amine compound of copper phthalocyanine / salt formation product (A)) of the amine compound of copper phthalocyanine to the salt formation product (A) is preferably 0.3 to 1.5.

When the mass ratio is within this range, fluorescence generated from the salt formation product (A) can be suppressed without impairing the dispersibility of the blue pigment. As a result, a color filter having high brightness and high contrast ratio can be achieved.

When the mass ratio is less than 0.3, the contrast is lowered because the inhibition of fluorescence and the dispersibility of the amine compound of copper phthalocyanine are insufficient. On the other hand, if the mass ratio exceeds 1.5, the color characteristic may be influenced, resulting in an undesirable effect. The more preferable mass ratio (amine compound / copper salt product (A) of copper phthalocyanine) is 0.4 to 1.2, and the most preferable mass ratio (amine compound / copper salt product (A) of copper phthalocyanine) is 0.5 to 1.1.

The blue coloring composition of this embodiment can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable compound and / or a photopolymerization initiator.

&Lt; Photopolymerizable compound >

In this embodiment, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

When the filter segment is formed by the photolithography method including the step of curing the composition by ultraviolet irradiation, the blue coloring composition for a color filter of the present invention may be prepared by adding a photopolymerization initiator or the like to the solvent- It can be prepared in the form of an alkali developing type coloring resist material.

<Increase / decrease>

The blue coloring composition for a color filter of this embodiment can contain a sensitizer in the same manner as in the first embodiment.

<Leveling agent>

To improve the leveling property of the composition on the transparent substrate, the leveling agent is preferably added to the blue coloring composition of this embodiment in the same manner as in the first aspect.

<Curing agent and hardening accelerator>

The blue coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary in order to assist curing of the thermosetting resin, as in the first embodiment.

&Lt; Other additive components >

In the blue coloring composition of the present embodiment, a storage stabilizer may be contained in the same manner as in the first embodiment, so that the viscosity of the composition is kept substantially constant over a long period of time. Further, in order to improve the adhesion with the transparent substrate, the adhesion improving agent such as a silane coupling agent may be contained in the same manner as in the first aspect.

<Antioxidant>

To increase the transmittance of the coating film, the coloring composition of the present invention preferably contains an antioxidant in the same manner as in the first aspect.

<Removal of Coarse Particles>

From the coloring composition of the present invention, it is preferable to remove coarse particles and entrained dust in the same manner as in the first aspect.

<Color filter>

The color filter of this embodiment is formed in the same manner as the first embodiment except that the blue coloring composition for a color filter of this embodiment is used.

The red filter segment can be formed using a conventional red coloring composition including a red pigment and a colorant carrier in the same manner as in the first embodiment.

In the red coloring composition, an orange color pigment and / or a yellow color pigment can be used together, as in the first aspect.

The green filter segment can be formed using a conventional green coloring composition including a green pigment and a colorant carrier in the same manner as in the first embodiment.

In the green coloring composition, a yellow pigment may be used in combination as in the first embodiment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free alumino-borosilicate glass, or resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for liquid crystal driving after paneling.

<Manufacturing Method of Color Filter>

The color filter of this embodiment can be produced by a printing method or a photolithography method in the same manner as in the first aspect.

(Example D)

Hereinafter, this embodiment will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, &quot; part &quot; means &quot; part by mass &quot;. The weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation). THF was used as a developing solvent. The specific surface area was measured by a BET method using nitrogen adsorption using an automatic vapor adsorption amount measuring apparatus ("BELSORP18" manufactured by Nippon Bell Co., Ltd.).

First, an acrylic resin solution (binder resin component), a finely divided pigment, a resin having a cationic group in its side chain, a salt formation product (A), a xanthene compound, a pigment derivative, a pigment dispersion, Solution, a xanthene-based compound-containing resin solution, a red resist material, and a green resist material.

&Lt; Process for producing acrylic resin solution >

(Preparation of acrylic resin solution 1D)

An acrylic resin solution 1D was prepared in the same manner as described for the acrylic resin solution 1A.

(Preparation of acrylic resin solution 2D)

An acrylic resin solution 2D was prepared by the same method as described for the acrylic resin solution 2A.

(Preparation of acrylic resin solution 3D)

An acrylic resin solution 3D was prepared by the same method as described for the acrylic resin solution 3A.

(Preparation of acrylic resin solution 4D)

An acrylic resin solution 4D was prepared in the same manner as described for the acrylic resin solution 4A.

&Lt; Production method of micronized pigment >

(Preparation of blue fine pigment 1D)

A blue fine pigment 1D was prepared in the same manner as described for the blue fine pigment 1A.

(Preparation of blue fine pigment 2D)

A blue fine pigment 2D was prepared by the same method as described for the blue fine pigment 2A.

(Production of purple fine pigment 1D)

A purple fine pigment 1D was prepared in the same manner as described for the purple fine pigment 1A.

(Preparation of red fine pigment 1D)

A red fine pigment 1D was prepared in the same manner as described for the red fine pigment 1A.

(Preparation of Yellow Fine Pigment 1D)

A yellow fine pigment 1D was prepared in the same manner as described for the yellow fine pigment 1A.

(Production of green fine pigment 1D)

A green fine pigment 1D was prepared in the same manner as described for the green fine pigment 1A.

(Preparation of yellow fine pigment 2D)

A yellow fine pigment 2D was prepared in the same manner as described for the yellow fine pigment 2A.

<Method for preparing resin having cationic group in side chain>

(Production of resin 1D having a cationic group in a side chain)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 DEG C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2 parts of 2,2'-azobis (2 , 4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were uniformly mixed, and the mixture was introduced into a dropping funnel. The dropping funnel was attached to a four-necked separable flask, and the mixed solution was dropped into the reaction vessel over 2 hours. From the resulting solid content after 2 hours from the completion of the dropwise addition, it was confirmed that a resin with a polymerization yield of 98% or more and a weight average molecular weight (Mw) of 6830 was obtained. Subsequently, the liquid containing the solid content was cooled to 50 DEG C, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was further reacted at 50 DEG C for 2 hours. Thereafter, the temperature was raised to 80 DEG C over 1 hour, and the reaction was further continued for 2 hours. Thus, Resin 1D having a cationic group in its side chain was obtained in the form of a resin solution having a resin component content of 47 mass%. The ammonium salt value of the obtained resin was 34 mgKOH / g.

The weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard material. The ammonium salt value of the resin having a cationic group in the side chain was determined by titrating with a 5% aqueous solution of potassium chromate as an indicator and titrating with 0.1 N of an aqueous solution of silver nitrate. The calculated value was converted into the equivalent amount of potassium hydroxide.

(Production of Resin 2D Having a Cationic Group in the Side Chain)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 62.4 parts of isopropyl alcohol, and the temperature was raised to 75 DEG C under a nitrogen stream. Separately from this, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2'-azobis ( 5.7 parts of 2,4-dimethylvaleronitrile) and 15.6 parts of methyl ethyl ketone were uniformly mixed, and the mixture was introduced into a dropping funnel. The dropping funnel was attached to a four-necked separable flask, and the mixed solution was dropped into the reaction vessel over 2 hours. From 2 hours after completion of the dropwise addition, it was confirmed that the resulting polymer had a polymerization yield of 98% or more and a weight-average molecular weight (Mw) of 7420. Subsequently, the liquid containing the solid content was cooled to 50 占 폚, and 72 parts of isopropyl alcohol was added thereto to obtain a resin 2D having a cationic group in the side chain in the form of a resin solution having a resin component content of 40 mass%. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Production of Resin 3D Having a Cationic Group in the Side Chain)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 DEG C under a nitrogen stream. Separately, 27.5 parts of isopropyl methacrylate, 25.0 parts of benzyl methacrylate, 27.5 parts of 2-ethylhexyl acrylate, 20.0 parts of N, N-dimethylaminomethylstyrene, 2,2'-azobis (2 , 4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were uniformly mixed, and the mixture was introduced into a dropping funnel. The dropping funnel was attached to a four-necked separable flask, and the mixed solution was dropped into the reaction vessel over 2 hours. From the solid content obtained after 2 hours from completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6770. Subsequently, the liquid containing the solid content was cooled to 50 DEG C, to which benzyl chloride (15.7 parts) and ethanol (22.0 parts) were added, followed by further reaction at 50 DEG C for 2 hours. Thereafter, the temperature was raised to 80 DEG C over 1 hour, and the reaction was further continued for 2 hours. Thus, a resin solution having a resin component of 50 mass% was obtained as the resin 3D having a cationic group in the side chain. The ammonium salt value of the obtained resin was 60 mgKOH / g.

(Production of Resin 4D Having a Cationic Group in the Side Chain)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 62.4 parts of isopropyl alcohol, and the temperature was raised to 75 DEG C under a nitrogen stream. Separately, 25.0 parts of methyl methacrylate, 25.0 parts of stearyl methacrylate, 20.0 parts of cyclohexyl methacrylate, 15.0 parts of blemish PE90 (niche-like agent, diethylene glycol monomethacrylate) 20.0 parts of vinylpyrrolidone, 4.7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol were uniformly mixed, and the mixture was introduced into a dropping funnel. The dropping funnel was attached to a four-necked separable flask, and the mixed solution was dropped into the reaction vessel over 2 hours. After 2 hours from the completion of the dropwise addition, it was confirmed from the resulting solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7550. Subsequently, the liquid containing the solid content was cooled to 50 DEG C, to which 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, followed by further reaction at 50 DEG C for 2 hours. Subsequently, the temperature was raised to 80 DEG C over 1 hour, and the reaction was further continued for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to this solution to obtain a resin 4D having a cationic group in the side chain in the form of a resin solution having a resin component of 44 mass%. The ammonium salt value of the obtained resin was 92 mgKOH / g.

(Production of resin 5D having a cationic group in the side chain)

A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 82.0 parts of methyl ethyl ketone, and the temperature was raised to 75 DEG C under a nitrogen stream. Separately, 23.5 parts of ethyl methacrylate, 26.0 parts of t-butyl methacrylate, 25.0 parts of lauryl methacrylate, 0.5 part of Kayamer PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mole of? -Caprolactone, 10.0 parts of hydroxyethyl methacrylate phosphate), 17.5 parts of diethylaminopropyl methacrylate, 6.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile), and 25.6 parts of methyl ethyl ketone were uniformly dispersed , And the mixture was charged into a dropping funnel. The dropping funnel was attached to a four-necked separable flask, and the mixed solution was dropped into the reaction vessel over 2 hours. After 2 hours from completion of the dropwise addition, it was confirmed from the resulting solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 7010. Subsequently, the liquid containing the solid content was cooled to 50 캜. Thus, a resin 5D having a cationic group in its side chain was obtained in the form of a resin solution having a resin component of 48 mass%. The amine salt value of the obtained resin was 49 mgKOH / g.

Herein, the amine value of the resin having a cationic group in the side chain was obtained by converting a value measured by the potentiometric titration method to an equivalent amount of potassium hydroxide by using a 0.1 N hydrochloric acid aqueous solution.

&Lt; Preparation method of salt formation product (A) >

(Preparation salt product (A-1D))

By the following procedure, C.I. (A-1D) comprising Acid Red 289 and Resin 1D having a cationic group in its side chain.

To 2000 parts of water was added a resin 1D having a cationic group in 51 parts of the side chain, and the mixture was sufficiently stirred and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 32 parts of C.I. (A-1D) of Acid Red 289 and Resin 1D having a cationic group in the side chain. To a solution of C.I. The content of effective dye component derived from Acid Red 289 was 29 mass%.

(Salt formation product (A-2))

By the following procedure, C.I. (A-2D) consisting of Acid Red 289 and Resin 2D having a cationic group in its side chain.

A resin 2D having a cationic group in 88 parts of side chains was added to 2000 parts of a 10% aqueous methanol solution, the mixture was sufficiently stirred, and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After completion of dropwise addition, the solution was stirred at 60 占 폚 for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 43 parts of C.I. (A-2D) of Acid Red 289 and Resin 2D having a cationic group in its side chain. To a solution of C.I. The content of the effective coloring matter component derived from the Acid Red 289 was 22% by mass.

(Salt formation product (A-3D))

By the following procedure, C.I. (A-3D) comprising an acid red 289 and a resin 3D having a cationic group in its side chain.

To 2000 parts of a 10% aqueous solution of N, N-dimethylformamide was added 46.3 parts of a resin 3D having a cationic group in its side chain. The mixture was stirred sufficiently and then heated to 70 占 폚. To this resin solution, 90 parts of water and 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After the completion of the dropwise addition, the mixture was stirred at 70 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 29 parts of C.I. (A-3D) of Acid Red 289 and Resin 3D having a cationic group in its side chain. The content of C.I. The content of effective dye component derived from Acid Red 289 was 30% by mass.

(Preparation salt product (A-4D))

By the following procedure, C.I. (A-4D) comprising an acid red 289 and a resin 4D having a cationic group in its side chain.

A solution in which resin 4D having a cationic group was dissolved in 1000 parts of water in 20.0 parts of side chains was prepared. This mixed solution was sufficiently stirred, and then heated to 70 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 19 parts of C.I. (A-4D) of Acid Red 289 and Resin 4D having a cationic group in its side chain was obtained. To a solution of C.I. The content of effective dye component derived from Acid Red 289 was 53 mass%.

(Preparation salt product (A-5D))

By the following procedure, C.I. (A-5D) comprising Acid Red 289 and a resin 5D having a cationic group in its side chain.

To 2000 parts of 20% acetic acid, 63.2 parts of resin 5D having a cationic group was added to the side chain. The mixture was stirred sufficiently, and then heated to 60 占 폚. As a result, the tertiary amino group of the side chain was converted to ammonium salt. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 38 parts of C.I. (A-5D) of Acid Red 289 and Resin 5D having a cationic group in its side chain. To a solution of C.I. The content of the effective coloring matter component derived from the Acid Red 289 was 23% by mass.

(Preparation salt product (A-6D))

By the following procedure, C.I. (A-6D) comprising Acid Red 289 and Disperbyk-2000 (manufactured by Big Chem Japan, modified acrylic block copolymer, ammonium salt content: 61 mg KOH / g) was prepared.

To 2000 parts of water was added 50.9 parts of Disperbyk-2000, the mixture was thoroughly stirred, and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 289 was added little by little dropwise. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 31 parts of C.I. (A-6D) of Acid Red 289 and Disperbyk-2000 was obtained. To a solution of C.I. The content of effective dye component derived from Acid Red 289 was 33% by mass.

(Preparation salt product (A-7D))

By the following procedure, C.I. (A-7D) comprising an acid red 52 and a resin 1D having a cationic group in its side chain.

To 2000 parts of water was added a resin 1D having a cationic group in 51 parts of the side chain, and the mixture was sufficiently stirred and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution obtained by dissolving the solid red 52 was dropped little by little. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 32 parts of C.I. (A-7D) was obtained between the acid red 52 and the resin 1D having a cationic group in the side chain. To a solution of C.I. The content of the effective dye component derived from the Acid Red 52 was 30 mass%.

(Preparation salt product (A-8D))

By the following procedure, C.I. (A-8D) comprising an acid red 87 and a resin 1D having a cationic group in its side chain.

To 2000 parts of water was added a resin 1D having a cationic group in 51 parts of the side chain, and the mixture was sufficiently stirred and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution prepared by dissolving solid red 87 was added dropwise little by little. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 32 parts of C.I. (A-8D) was obtained from the acid red 87 and the resin 1D having a cationic group in the side chain. To a solution of C.I. The content of effective dye component derived from Acid Red 87 was 28% by mass.

(Preparation salt product (A-9D))

By the following procedure, C.I. (A-9D) comprising an acid red 92 and a resin 1D having a cationic group in its side chain.

To 2000 parts of water was added a resin 1D having a cationic group in 51 parts of the side chain, and the mixture was sufficiently stirred and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. An aqueous solution obtained by dissolving an aqueous solution of Acid Red 92 was dropped little by little. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 32 parts of C.I. (A-9D) was obtained from the acid red 92 and the resin 1D having a cationic group in the side chain. A solution of C.I. The content of effective dye component derived from Acid Red 92 was 29 mass%.

(Preparation salt product (A-10D))

By the following procedure, C.I. (A-10D) comprising Acid Red 388 and Resin 1D having a cationic group in its side chain.

To 2000 parts of water was added a resin 1D having a cationic group in 51 parts of the side chain, and the mixture was sufficiently stirred and then heated to 60 占 폚. To 90 parts of water, 10 parts of C.I. And an aqueous solution prepared by dissolving solid red 388 was added dropwise little by little. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 32 parts of C.I. (A-10D) was formed of the acid red 388 and the resin 1D having a cationic group in the side chain. To a solution of C.I. The content of effective dye component derived from Acid Red 388 was 30% by mass.

(Salt formation product (A-11D))

By the following procedure, C.I. (A-11D) comprising an acid red 52 and a resin 5D having a cationic group in its side chain.

To 2000 parts of 20% acetic acid, 63.2 parts of resin 5D having a cationic group was added to the side chain. The mixture was stirred sufficiently, and then heated to 60 占 폚. As a result, the tertiary amino group of the side chain was converted to ammonium salt. To 90 parts of water, 10 parts of C.I. An aqueous solution obtained by dissolving the solid red 52 was dropped little by little. After completion of the dropwise addition, the mixture was stirred at 60 DEG C for 120 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, water was removed from the crude product remaining on the filter paper using a drier, and 38 parts of C.I. (A-11D) was obtained from the acid red 52 and the resin 5D having a cationic group in the side chain. The amount of C.I. The content of the effective dye component derived from the Acid Red 52 was 22 mass%.

&Lt; Method for producing xanthan family compound >

(Xanthene compounds (C-1D) and (C-2D))

The xanthene compounds (C-1A) and (C-2A) of the first embodiment were used as the xanthene compounds (C-1D) and (C-2D), respectively.

&Lt; Production method of pigment derivative >

(Production of pigment derivative 1D (basic compound of copper phthalocyanine)

30 parts of copper phthalocyanine was added to 300 parts of chlorosulfonic acid, and this was completely dissolved. Then, 24 parts of thionyl chloride was added to this solution, the temperature was gradually raised, and the reaction was carried out at 101 ° C for 3 hours. Subsequently, the reaction solution was poured into 9,000 parts of ice water, stirred, filtered and rinsed. The obtained press cake was dispersed in 300 parts of water to prepare a slurry. To this slurry, 15 parts of N, N-dimethylaminopropylamine was added and the mixture was stirred at room temperature for 3 hours and then stirred at 60 DEG C for 2 hours. Thereafter, filtration, washing with water and drying were carried out to obtain 36 parts of a copper phthalocyanine sulfonic acid amide compound. The resulting copper phthalocyanine sulfonic acid amide compound was subjected to a compositional analysis by a liquid chromatograph mass spectrometry platform LCZ manufactured by Waters Corporation and it was found that copper phthalocyanine sulfonic acid having one substituent of the following formula (22) Amide compound and a copper phthalocyanine sulfonic acid amide compound having two substituents of the following formula (22) in a mass ratio of 85:15. This copper phthalocyanine sulfonic acid amide compound is referred to as a pigment derivative 1D.

Equation (22):

CuPc: copper phthalocyanine residue

&Lt; Production method of pigment dispersion >

(Preparation of pigment dispersion (DP-1D)) [

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours using Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the mixture was filtered through a 5.0 탆 filter to obtain a pigment dispersion (DP-1).

Blue Fine Pigment 1D (CI Pigment Blue 15: 6): 11.0 parts

Dye derivative 1D: 1.0 part

Acrylic resin solution 1D: 39.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Chiba Japan): 1.0 part

(Preparation of pigment dispersions (DP-2D) to (DP-7D)

Pigment dispersions (DP-2D) to (DP-7D) were prepared in the same manner as in the pigment dispersion (DP-1D) except that the blue fine pigment 1D was changed to the pigment shown in Table 19. When the dye derivative 1D is not contained, 40 parts of the acrylic solution resin is used.

&Lt; Preparation method of a resin solution containing a salt formation product and a resin solution containing a xanthene compound >

(Preparation of a salt solution-containing resin solution (DA-1D)) [

The following mixture was stirred so as to be homogeneous and then filtered with a 5.0 탆 filter to obtain a resin solution (DA-1D) containing the salt formation product.

Preparation salt product (A-1D): 11.0 parts

Acrylic resin solution 1D: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Preparation of a salt solution-containing resin solution (DA-1D)) [

Containing resin solution (DA-1D) was obtained in the same manner as in the above-described formation product containing resin solution (DA-1D) except that the titled product (A-1D) was changed to the cosmetic product (A) (DA-2D) to (DA-11D) and a xanthene-based compound-containing resin solution (DC-1D) and (DC-2D) were prepared. The content of the pigment component is shown in Table 20. The dye content A indicates the content (mass%) of the effective dye component in the salt formation product (A) or the xanthene-based compound. The coloring matter content B represents the content (mass%) of the effective coloring matter component in the coloring agent-containing resin solution.

* 1 Dye content component content A: Content of effective dye component (% by weight) of the crude product (A) or xanthene-

* 2 Content of coloring matter component B: Content of effective coloring matter component (% by weight) in resin solution containing coloring agent

&Lt; Preparation method of red and green resist material >

(Preparation of red resist material)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain a red resist material.

Pigment dispersion (DP-4D): 50.0 parts

Pigment dispersion (DP-5D): 10.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

(Preparation of green resist material)

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain a green resist material.

Pigment dispersion (DP-6D): 45.0 parts

Pigment dispersion (DP-7D): 15.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Ethylene glycol monomethyl ether acetate: 23.2 parts

[Examples 1D to 14D, Comparative Examples 1D to 4D]

(Example 1D: Coloring composition (DB-1D))

The following mixture was stirred so as to be homogeneous, and then filtered with a 5.0 占 퐉 filter to obtain a mixed colored composition.

Colorant-containing resin solution (DA-1D): 2.2 parts

Pigment dispersion (DP-1D): 8.8 parts

Acrylic resin solution 1D: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Examples 2D to 14D, Comparative Examples 1D to 4D: Coloring compositions (DB-2D) to (DB-18D))

(DB-2D) to (DB-18D) were prepared in the same manner as the coloring composition (DB-1D) except that the coloring agent-containing resin solution (DA- .

(Evaluation of color characteristics)

The coloring composition was coated on a glass substrate. Specifically, the color compositions according to Examples 1D to 11D and Comparative Examples 1D to 3D were applied in such a thickness that the chromaticity under the C light source was x = 0.150 and y = 0.060. The coloring compositions according to Examples 12D to 14D and Comparative Example 4D were applied in such a thickness that the chromaticity under the C light source was x = 0.190 and y = 0.060. Then, these substrates were heated at 230 占 폚 for 20 minutes to form a coloring layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Table 22 shows the results.

(Method of foreign matter test on coated film)

The above coloring composition was evaluated for ease of occurrence of coating irregularity due to foreign matter. Specifically, first, the coloring composition was applied on a transparent substrate so that the dry film thickness was about 2.0 占 퐉, and this was heated in an oven at 230 占 폚 for 20 minutes to obtain a test substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five visual fields, the number of observable particles was counted, and the total number of particles was obtained. Table 22 shows the results.

In Table 22, symbols used in the column of &quot; foreign matter on the coating film &quot; mean the following.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

When the total number of particles is less than 20, coating irregularities caused by foreign matters hardly occur. When the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. When the total number of particles is 100 or more, coating unevenness (smudge) due to foreign matter occurs.

The coating film obtained from the coloring composition containing the blue pigment and the salt formation product (A) had few foreign matters (undissolved foreign matters). On the other hand, the coating film obtained from the coloring composition containing the xanthene compounds (C-1D) and (C-2D) had a very large number of foreign substances. That is, when a salt-forming product of a resin having a cationic group in the side chain was used, superior performance could be achieved as compared with the case of using a xanthene dye substituted with a functional group.

In addition, the coating film obtained from the coloring composition containing the blue pigment and the salt formation product (A) had a high brightness. The brightness of the coating film according to the comparative example was lower than that of the coating film according to the example.

[Examples 15D to 27D and Comparative Examples 5D to 7D]

(Example 15D: Resist material (R-1D)) [

The following mixture was stirred so as to be uniform, and then filtered with a filter of 1.0 탆 to obtain an alkali development type resist material (R-1D).

Colorant-containing resin solution (DA-1D): 12.0 parts

Pigment dispersion (DP-1D): 48.0 parts

Acrylic resin solution 1D: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Examples 16D to 27D and Comparative Examples 5D to 7D: Resist materials (R-2D) to (R-16D)

(R-2D) to (R-1) were prepared in the same manner as in the resist material (R-1D) except that the colorant-containing resin solution and the coloring agent dispersion and the blending amounts thereof were changed as shown in Table 23 -16D).

(Examples 28D to 33D: Resist materials (R-17D) to (R-22D)) [

(R-17D), (R-18D) and (R-17D) were prepared in the same manner as the resist material (R-5D) except that the acrylic resin solution 1D was changed to the acrylic resin solutions 2D, R-19D). (R-20D) and (R-21D) were prepared in the same manner as the resist material (R-11D) except that the acrylic resin solution 1D was changed to acrylic resin solutions 2D, And (R-22D), respectively.

(Evaluation of resist material)

A coating film was formed from the resist materials (R-1D) to (R-22D), and the chromaticity, the amount of foreign matter, the heat resistance, the light resistance, the solvent resistance and the contrast ratio were examined for each of these coating films by the following methods. The results of the test are shown in Table 24.

(Method of foreign matter test on coated film)

The above resist material was evaluated for ease of occurrence of coating irregularity caused by foreign matter. Specifically, first, a resist material was applied on a transparent substrate so that the dry film thickness was about 2.5 占 퐉, and the entire surface of the coated film was exposed with ultraviolet rays. Thereafter, this was heated in an oven at 230 DEG C for 20 minutes and then cooled to obtain an evaluation substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was set to 500 times and observed in the transmission mode. Then, for any five visual fields, the number of identifiable particles was counted, and the total number of particles was obtained. The results are shown in Table 24.

In Table 24, the meanings of the symbols described in the column of &quot; foreign matter on the coating film &quot; are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

(Evaluation of color characteristics)

A resist material was applied on the glass substrate. Specifically, the above resist material was coated with a film thickness such that the chromaticity under the C light source was x = 0.150, y = 0.060. These substrates were heated at 230 占 폚 for 20 minutes to form a colored layer on the substrate. Thereafter, the brightness Y of the substrate on which the colored layer was formed was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Table 24 shows the results.

(Method of coating film heat resistance test)

The resist material was coated on the transparent substrate so that the dry film thickness became about 2.5 占 퐉, and the coating film was exposed to ultraviolet rays through a mask having a predetermined pattern. This coating film was sprayed with an alkali developing solution to remove the uncured portions to form a desired pattern. This was then heated in an oven at 230 占 폚 for 20 minutes. After cooling down, the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film under a C light source was measured using a brown spectrophotometer (OSP-SP200 manufactured by Olympus Kogaku Co., Ltd.) . Thereafter, this was provided to a heat resistance test in which the plate was heated in an oven at 250 DEG C for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured.

Using these chromaticity values, the color difference? Eab * was calculated by the following calculation formula. Then, based on the color difference? Eab *, the heat resistance of the coating film was evaluated in the following four stages.

?:? Eab * is less than 1.5

?:? Eab * was 1.5 or more and less than 2.5

DELTA: Eab * is not less than 2.5 and not more than 5.0

X:? Eab * was 5.0 or more

Table 24 shows the results.

(Method of coating film light resistance test)

(1), a * (1) and b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.) Quot;). Thereafter, the substrate was placed in a light resistance tester (&quot; SUNTEST CPS + &quot; manufactured by TOYOSEIKI), and left for 500 hours. After removal of the substrate, chromaticity 2 (L * (2), a * (2), b * (2)) under a C light source was measured. Using these chromaticities, the color difference (ΔEab *) was calculated in the same manner as in the coating film heat resistance test, and the light resistance of the coating film was evaluated based on the same criteria as the heat resistance. Table 24 shows the results.

(Method of solvent resistance test)

(L * (1), a * (1), b * (1)) under a C light source were measured with a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., ). Subsequently, the substrate was immersed in N-methylpyrrolidone for 30 minutes. (2) (L * (2), a * (2), b * (2)) under a C light source were measured and the color difference (? Eab *) was measured in the same manner as in the coating film heat resistance test, And the solvent resistance of the coating film was evaluated based on the same criteria as the heat resistance. Table 24 shows the results.

(Contrast ratio evaluation)

The contrast ratio of the colored layer formed in the evaluation of color characteristics was measured by the following method. The results are shown in Table 24.

(Measurement method of contrast ratio of coating film)

The light emitted from the backlight unit for liquid crystal display is made incident on the first polarizing plate and the linearly polarized light transmitted through the first polarizing plate is transmitted through the dried coating film of the coloring composition and is made incident on the second polarizing plate. When the transmission axes of the first and second polarizing plates are parallel to each other (corresponding to the white display) and the transmission axes of the first and second polarizing plates are orthogonal to each other ). The contrast ratio is a ratio of the luminance when the transmission axes of the first and second polarizing plates are parallel to the luminance when the transmission axes thereof are orthogonal.

In this case, a color intensity meter ("BM-5A", Topcon Co.) is used as the luminance meter, and "NPF-G1220DUN" manufactured by Nitto Denko Co., Ltd. is used as the first and second polarizers. To measure the luminance, a black mask having holes having a length of 1 cm and a length of 1 cm is superimposed on the second polarizing plate so as to block unwanted light, and the measurement is performed with respect to the area corresponding to this hole.

Further, the linearly polarized light is changed into elliptically polarized light when it is transmitted through the dried coating film of the coloring composition, for example, when it is scattered by the pigment particles. As a result, when the transmission axes of the first and second polarizing plates are parallel, the amount of light transmitted through the second polarizing plate is reduced, that is, when scattering occurs due to the pigment in the coating film, the luminance when the transmission axes are parallel decreases, Since the brightness when the axes are orthogonal increases, the contrast ratio is lowered.

The coating films obtained from the resist materials (R-1D) to (R-12D) and (R-14D) to (R-19D) achieved satisfactory performance with respect to the contrast ratio, brightness and light resistance. Further, the coating film obtained from the resist material (R-13D) had a slightly low heat resistance, light resistance and solvent resistance, but had no problems for use in a color filter and had excellent color characteristics.

On the other hand, the coating film obtained from the resist materials (R-14D) and (R-15D) had many foreign matters and had a low contrast ratio.

The coating film obtained from the resist material (R-16D) of Comparative Example 7D had a lower brightness Y than the coating films of Examples 15D to 33D.

Further, as can be seen from the results of resist materials (R-17D) to (R-22D), foreign matter on the coating film could be further reduced by using an active energy ray curable resin having an ethylene bond.

[Example 34D]

(Color filter (CF-1D))

A black matrix as a light-shielding pattern was formed on a glass substrate, and then a red resist material was applied using a spin coater. The red resist material was applied in such a thickness that the chromaticity under the C light source was x = 0.640, y = 0.330. This coating film was irradiated with ultraviolet rays at an exposure dose of 300 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was subjected to a spraying development using an alkali developing solution comprising an aqueous solution of sodium carbonate of 0.2 mass% to remove unexposed portions, and the coating was washed with ion-exchanged water. Further, this substrate was heated at 230 DEG C for 20 minutes to form a red filter segment.

Next, a green resist material was applied to the substrate by the same method as described above. The green resist material was applied in such a thickness that the chromaticity under the C light source was x = 0.300 and y = 0.600. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a green filter segment.

Further, a blue resist material (R-1D) was coated on this substrate by the same method as described above. The blue resist material (R-1D) was applied in such a thickness that the chromaticity under the C light source was x = 0.150 and y = 0.060. This coating film was subjected to the same exposure, development, cleaning and firing as described above for the red filter segment to form a blue filter segment. Thus, a color filter CF-1D was obtained.

(Production of liquid crystal display)

An electrode made of ITO was formed on the color filter CF-1D, and an orientation layer made of polyimide was formed thereon. In addition, a TFT array and a pixel electrode were formed on one surface of a glass substrate prepared separately, and an orientation layer made of polyimide was formed thereon.

Next, on the surface provided with the electrodes of one of the glass substrates, a rim-shaped pattern having a passage communicating between the inside and the outside of the rim was formed by using a sealant. Subsequently, these substrates were stuck together with the spacer beads interposed therebetween such that the electrodes faced each other.

Subsequently, the liquid crystal composition was injected into the internal space of the thus obtained cell from the above passage. After sealing the passageway, a polarizing plate was attached to both sides of the cell to obtain a liquid crystal display panel.

Thereafter, a liquid crystal display was completed by combining a liquid crystal display panel and a backlight unit including three-wavelength CCFL.

[Examples 35D to 52D and Comparative Examples 8D to 10D]

(Color filters CF-2D to CF-22D)

(CF-2D) to (CF-22D) and a liquid crystal display in the same manner as the color filter (CF-1D) and the liquid crystal display, except that the resist material was changed to the resist material shown in Table 25 .

The color image was displayed on the liquid crystal display, and the brightness of the area corresponding to the red, green, and blue filter segments was measured using a brown spectrophotometer ("OSP-SP200" manufactured by Olympus Kogaku Co., Ltd.). Then, the brightness of the white display was obtained from these brightness values. The results are shown in Table 25.

Color filters (CF-1D) to (CF-13D) and (CF-17D) to (CF-22D) are formed from a resist material containing a blue pigment and a salt formation product (A). On the other hand, the color filter (CF-16D) is formed from a resist material containing a copper phthalocyanine pigment and a dioxazine-based pigment. A liquid crystal display including color filters CF-1D to CF-13D and CF-17D to CF-22D has a color filter CF-16D, The white image can be displayed at a higher brightness than the liquid crystal display including the liquid crystal display. In addition, the color filters CF-14D and CF-15D have high brightness but are not practical because of a large number of foreign objects as described above.

The techniques described in the first to fourth aspects can be combined with each other. For example, as the compound having a cationic group, two or more of a quaternary ammonium salt, an amine, and a resin having a cationic group may be used in combination. Further, the blue coloring composition according to the first, third and fourth aspects may contain the copper phthalocyanine described in the second aspect.

(Example 61D)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain an alkali development type resist material (R-61D).

Salt solution containing resin solution (DA-1D): 12.0 parts

Pigment dispersion (DP-1D): 48.0 parts

Acrylic resin solution 1D: 10.5 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]: 0.5 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

Evaluation similar to that performed on the resist material (R-1D) was performed except that this resist material (R-61D) was used. As a result, the brightness Y was 6.9 and the contrast ratio was 9,600. In addition, good results (?) Were obtained in all of the coating film foreign matters, heat resistance, light resistance and solvent resistance evaluation. Comparing the results obtained for the resist materials (R-61D) and (R-1D), it can be seen that the use of the antioxidant can improve the brightness and the contrast ratio.

○ The fifth sun

Next, the fifth aspect will be described.

Background Art [0002] Conventionally, a blue coloring composition containing a dioxazine-based pigment is used as a purple pigment in the production of a blue filter segment. In order to obtain a blue filter segment thin and having excellent color purity from such a blue coloring composition, up to now, the pigment content in the blue filter segment has been increased.

However, in order to increase the color difference from the green filter segment, the blue filter segment formed so that the spectral transmittance in the region near the wavelength of 570 nm is 3% or less has a maximum value of the spectral transmittance in the region near the wavelength of 450 nm , And blue color reproducibility is low. Thus, it is difficult to obtain a blue filter segment which exhibits a high transmittance in the blue wavelength region and a sufficiently reduced transmittance in the green and red wavelength regions.

The blue coloring composition for a color filter according to the fifth aspect contains a binder resin and a colorant. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed from a compound having a cationic group and a xanthene acid dye. By using such a blue coloring composition, a blue filter segment having desired optical characteristics can be easily realized.

That is, the coating film formed from the blue coloring composition according to the present embodiment so as to have a spectral transmittance of 3% at a wavelength of 570 nm has a spectral transmittance of 50% within a range of 490 to 510 nm, a spectral transmittance at a wavelength of 450 nm Is 85% or more, and the spectral transmittance at a wavelength of 540 nm is 11% or less. Such a coating film is preferably a dioxazine-based pigment such as C.I. Pigment Violet 23 was used instead of the salt formation product to obtain a coloring composition having a spectral transmittance of 3% at a wavelength of 570 nm. As a result, a spectral transmittance was high in a region near a wavelength of 450 nm, Exhibits a low spectral transmittance. Thus, the blue filter segment formed from the blue coloring composition according to this embodiment has a high maximum value of the spectral transmittance in the region near the wavelength of 450 nm. Therefore, this blue filter segment is very excellent in color reproduction in the blue region.

That is, in order to sufficiently reduce the transmittance in the green wavelength region, when the blue filter segment is formed such that the transmittance in the region near the wavelength of 570 nm is about 3% from the blue coloring composition according to this embodiment, Can have a low transmittance even in a region near a wavelength of 650 nm.

Alternatively, in order to sufficiently reduce the transmittance in the green wavelength region, when the blue filter segment is formed so that the transmittance in the region near the wavelength of 540 nm is about 10% from the blue coloring composition according to the present embodiment, Can have a high transmittance in a region near a wavelength of 450 nm.

As described above, according to this embodiment, it is possible to obtain a blue filter segment having a high transmittance in the blue wavelength region and a sufficiently reduced transmittance in the green and red wavelength regions.

<Preparation salt product (A)>

(The compound (a) having a cationic group)

The compound having a cationic group is not particularly limited as long as it is a compound having at least one onium base. The compound having an onium base is preferably an ammonium salt compound, an iodonium salt compound, a sulfonium salt compound, a diazonium salt compound, or a phosphonium salt compound.

The compound having a cationic group is preferably a resin (a1) having a cationic group in the side chain or a quaternary ammonium compound (a2) represented by the general formula (23).

The preferred form of the compound (a) having a cationic group is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more, in the entire wavelength range of 400 to 700 nm which is a visible light region. That is, it is preferable that the compound (a) having a cationic group does not inhibit the color development of the dye component and does not cause color change.

[Resin (a1) having cationic group in side chain]

As the resin (a1) having a cationic group in the side chain, the resin (a1) having a cationic group in the side chain of the fourth aspect may be used in the same manner.

[Quaternary ammonium compound (a2) represented by the general formula (23)] [

As the quaternary ammonium compound (a2) represented by the general formula (23), the quaternary ammonium compound of the first aspect can be used in the same manner.

The general formula (23)

[In the general formula (23), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion.]

Among them, the quaternary ammonium compound (a2) represented by the general formula (23) is a compound wherein R ₁ to R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, 20 &lt; / RTI &gt;

(Xanthene acid dye)

As the xanthene acid dye for obtaining the salt formation product (A), the xanthene acid dye of the first embodiment can be used in the same manner.

(Condensation treatment)

[Salt Formation of Resin (a1) Having Cationic Group in Side Chain and Xanthan Acidic Dye]

(A1) having a cationic group in a side chain and a salt-forming product comprising a xanthene acid dye can be obtained by the same method as described in the paragraph of "(salt formation)" in the fourth aspect.

The ratio of the resin (a1) having a cationic group in the side chain to the xanthene acid dye is preferably such that the total cation unit of the resin and the total anion of the xanthene acid dye It is preferable to set the molar ratio of the taper to be in the range of 10/1 to 1/4, and it is more preferable to set the molar ratio to be in the range of 2/1 to 1/2.

[Formation of salt of quaternary ammonium compound (a2) with xanthene acid dye]

The crude product of the xanthene acid dye and the quaternary ammonium compound (a2) can be obtained by the same method as described in the first aspect.

(The content of the effective coloring matter component contained in the salt formation product (A)

The content of the effective coloring matter component derived from the xanthine acid dye in the salt formation product (A) is the same as in the fourth aspect.

<Blue pigment>

As the blue pigment constituting the colorant, a phthalocyanine-based pigment and / or a triarylmethane-based lake pigment or the like is used in the same manner as in the first embodiment. As the phthalocyanine-based pigment, it is preferable to use a copper phthalocyanine blue pigment.

Among these, C.I. Pigment Blue 15: 6 or C.I. Pigment Blue 1 is preferably used.

(Fineness of pigment)

The blue pigment used in the blue coloring composition of the present invention and other optional pigments can be finely ground by a salt milling treatment as in the second embodiment.

The primary particle diameter of the pigment is measured by a method in which the size of the primary particle is directly measured from an electron microphotograph of the pigment by a TEM (transmission electron microscope), similarly to the second aspect.

The salt formation product (A) is preferably used in an amount of 1 to 800 parts by mass, more preferably 5 to 400 parts by mass, per 100 parts by mass of the blue pigment. If the addition amount of the salt formation product (A) is less than 1 part by mass, reproducible chromaticity regions become narrow. When the added amount exceeds 800 parts by mass, the color is changed.

Considering the color structure, the content of the effective coloring matter component in the salt formation product (A) is preferably in the range of 1 to 400 parts by mass with respect to 100 parts by mass of the blue pigment. The mass of the effective dye component in the salt formation product (A) is more preferably in the range of 5 to 300 parts by mass, particularly preferably in the range of 17 to 300 parts by mass with respect to 100 parts by mass of the blue pigment.

Particularly, as a xanthene acid dye, C.I. Acid Red 289 or C.I. The salt formation product (A) using the acid red 52 is excellent in solvent solubility and achieves excellent heat resistance, light resistance and solvent resistance when used in combination with a blue pigment. The reason why the salt formation product (A) is used in combination with the blue pigment to achieve good performance is that the salt formation product (A) is adsorbed on the blue pigment while being dissolved or dispersed in the solvent.

&Lt; Other coloring agents >

In the blue coloring composition of the present embodiment, other organic pigments may be added to the blue coloring composition in addition to the components of the coloring agent, as long as they do not interfere with obtaining the effect, for coloring purposes, as in the first embodiment.

<Binder Resin>

The binder resin is to disperse the coloring agent, in particular the crude salt product, or to dye or penetrate the crude product. Examples of the binder resin include a thermoplastic resin and a thermosetting resin, and the "resin" of the first aspect can be used in the same manner.

<Organic solvents>

In the blue coloring composition of the present invention, the coloring agent is sufficiently dispersed or dissolved in the coloring agent carrier to form a filter segment on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 占 퐉 Solvents may be included for ease of handling.

As the organic solvent, the solvent of the first aspect may be used in the same manner.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like are preferable since the dispersibility and solubility of the pigment and the salt formation product (A) , Aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone are preferably used. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and hygiene and low viscosity.

These organic solvents may be used singly or in combination of two or more kinds. When two or more kinds of solvents are mixed, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95 mass%.

The organic solvent is used in an amount of 800 to 4000 parts by mass based on 100 parts by mass of the total mass of the coloring agent from the viewpoint of forming a filter segment having a desired uniform film thickness by adjusting the coloring composition to an appropriate viscosity desirable.

<Dispersion>

The blue coloring composition of the present invention is a blue coloring composition comprising a coloring agent containing a coloring agent (A) obtained by reacting a blue pigment and a resin having a cationic group in a side chain with a xanthene acid dye and a colorant comprising a binder resin and a solvent To a treatment using various dispersion means such as 3 roll mill, 2 roll mill, sand mill, kneader, and stirrer, together with a dispersion aid such as a pigment derivative, preferably in a carrier. The blue coloring composition of the present embodiment may be produced by dispersing a blue pigment, a salt formation product (A) and other coloring agents in a coloring agent carrier, and then mixing them.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, as in the fourth aspect, a dispersion aid such as a pigment derivative, a resinous dispersant, and a surfactant can be appropriately used.

As the pigment derivative, the pigment derivative of the fourth aspect may be used in the same manner.

As the resinous dispersant, the resinous dispersant of the first aspect may be used in the same manner.

As the surfactant, the surfactant of the first aspect may be used in the same manner.

The blue coloring composition of this embodiment can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable compound and / or a photopolymerization initiator.

&Lt; Photopolymerizable compound >

In this embodiment, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

When the filter segment is formed by the photolithography method including curing the composition by ultraviolet irradiation, the blue coloring composition for a color filter of the present invention may be prepared by adding a photopolymerization initiator or the like to a solvent- It can be prepared in the form of a development type coloring resist material.

<Increase / decrease>

The blue coloring composition for a color filter of this embodiment can further contain a sensitizer in the same manner as in the first embodiment.

<Leveling agent>

To improve the leveling property of the composition on the transparent substrate, the leveling agent is preferably added to the blue coloring composition of this embodiment in the same manner as in the first aspect.

<Curing agent, hardening accelerator>

The blue coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as necessary in order to assist curing of the thermosetting resin, as in the first embodiment.

&Lt; Other additive components >

In the blue coloring composition of the present embodiment, a storage stabilizer may be contained in the same manner as in the first embodiment, so that the viscosity of the composition is kept substantially constant over a long period of time. Also, in order to improve the adhesion with the transparent substrate, the adhesion improver may be contained in the same manner as in the first embodiment.

<Antioxidant>

To increase the transmittance of the coating film, the coloring composition of the present invention preferably contains an antioxidant in the same manner as in the first aspect.

&Lt; Process for producing colored composition for color filter &

The blue coloring composition for a color filter of the present invention can be obtained by, for example, performing a process of kneading a mixture containing a binder resin, a coloring agent and the above optional components by a two-roll mill to form a sheet material a plurality of times, , Followed by adding the chip obtained by the above to an organic solvent, stirring the mixture, and subjecting the mixture to a dispersion treatment using a media disperser such as a bead mill. Alternatively, the blue coloring composition for a color filter of the present invention may be obtained by preparing a blue coloring composition by providing the above mixture to a dispersion treatment using a media dispersing machine such as a bead mill, and adding a photopolymerizable compound, a photopolymerization initiator, .

From this colored composition, coarse particles of 5 mu m or more, preferably coarse particles of 1 mu m or more, more preferably coarse particles of 0.5 mu m or more, and dust particles of mixed dust or the like are removed by means of centrifugation, sintering filter, It is preferable to carry out the removal.

<Color filter>

Next, the color filter of this embodiment will be described.

The color filter according to this aspect includes, for example, a plurality of filter segments that are different in absorption spectrum, and are typically arranged in a regular fashion. One form of the color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter according to the present embodiment, for example, the blue filter segment is formed from the above-mentioned coloring composition for a color filter.

The red filter segment can be formed by using a conventional red coloring composition including a red pigment and a pigment carrier in the same manner as in the first embodiment. In the red coloring composition, an orange color pigment and / or a yellow color pigment may be used together in the same manner as in the first aspect.

The green filter segment can be formed by using a conventional green coloring composition including a green pigment and a pigment carrier in the same manner as in the first embodiment. In the green coloring composition, yellow pigments can be used in combination as in the first embodiment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free alumino-borosilicate glass, or resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for liquid crystal driving after paneling.

<Manufacturing Method of Color Filter>

The color filter of this embodiment can be produced by a printing method or a photolithography method in the same manner as in the first aspect.

(Example E)

Hereinafter, this embodiment will be described on the basis of embodiments, but the present invention is not limited thereto. Unless otherwise specified, &quot; part &quot; means &quot; part by mass &quot;. The weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation). THF was used as a developing solvent.

The weight average molecular weight (Mw) of the acrylic resin was measured with a GPC (HLC-8120GPC, manufactured by Tosoh Corporation) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation) Weight average molecular weight (Mw) in terms of conversion.

First, an acrylic resin solution, a finely divided pigment, a resin having a cationic group in its side chain, a salt formation product (A), a xanthene compound, a pigment dispersion, a resin solution containing a salt formation product, a resin solution containing a xanthene compound , A red resist material, and a green resist material are described.

&Lt; Process for producing acrylic resin solution >

(Preparation of acrylic resin solution 1E)

An acrylic resin solution 1E was prepared in the same manner as described for the acrylic resin solution 1A.

(Preparation of acrylic resin solution 2E)

An acrylic resin solution 2E was prepared in the same manner as described for the acrylic resin solution 2A.

(Preparation of acrylic resin solution 3E)

An acrylic resin solution 3E was prepared by the same method as described for the acrylic resin solution 3A.

(Preparation of acrylic resin solution 4E)

An acrylic resin solution 4E was prepared in the same manner as described for the acrylic resin solution 4A.

&Lt; Production method of micronized pigment >

(Preparation of blue fine pigment 1E)

A blue fine pigment 1E was prepared in the same manner as described for the blue fine pigment 1A.

(Preparation of blue fine pigment 2E)

A blue fine pigment 2E was prepared in the same manner as described for the blue fine pigment 2A.

(Production of purple fine pigment 1E)

A purple fine pigment 1E was prepared in the same manner as described for the purple fine pigment 1A.

<Method for preparing resin (a1) having cationic group in side chain>

(Preparation of Resin 1E Having a Cationic Group in the Side Chain)

Resin 1E having a cationic group in its side chain was prepared by the same method as described for Resin 1D.

(Preparation of Resin 2E Having a Cationic Group in the Side Chain)

Resin 2E having a cationic group in its side chain was prepared by the same method as described for Resin 2D.

(Preparation of Resin 3E Having a Cationic Group in the Side Chain)

Resin 3E having a cationic group in the side chain was prepared by the same method as described for Resin 3D.

(Preparation of Resin 4E Having a Cationic Group in the Side Chain)

Resin 4E having a cationic group in its side chain was prepared by the same method as described for Resin 4D.

(Preparation of Resin 5E Having a Cationic Group in the Side Chain)

A resin 5E having a cationic group in the side chain was prepared by the same method as described for the resin 5D.

&Lt; Preparation of crude salt product >

(Preparation salt product (A-1E))

The salt formation product (A-1E) was prepared in the same manner as described for the salt formation product (A-1D).

(Preparation salt product (A-2E))

The salt formation product (A-2E) was prepared in the same manner as described for the salt formation product (A-2D).

(Preparation salt product (A-3E))

The salt formation product (A-3E) was prepared in the same manner as described for the salt formation product (A-3D).

(Preparation salt product (A-4E))

The salt formation product (A-4E) was prepared in the same manner as described for the salt formation product (A-4D).

(Preparation salt product (A-5E))

The salt formation product (A-5E) was prepared in the same manner as described for the salt formation product (A-5D).

(Preparation salt product (A-6E))

The salt formation product (A-6E) was prepared in the same manner as described for the salt formation product (A-6D).

(Preparation salt product (A-7E))

The salt formation product (A-7E) was prepared in the same manner as described for the salt formation product (A-7D).

(Preparation salt product (A-8E))

The salt formation product (A-8E) was prepared in the same manner as described for the salt formation product (A-8D).

(Preparation salt product (A-9E))

The salt formation product (A-9E) was prepared in the same manner as described for the salt formation product (A-9D).

(Preparation salt product (A-10E))

The salt formation product (A-10E) was prepared in the same manner as described for the salt formation product (A-10D).

(Preparation salt product (A-11E))

The salt formation product (A-11E) was prepared in the same manner as described for the salt formation product (A-11D).

(Preparation salt product (A-12E))

By the following procedure, C.I. (A-12E) comprising Acid Red 289 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-12E) which is a product salt product of Acid Red 289 and distearyldimethylammonium chloride. To a solution of C.I. The content of effective dye component derived from Acid Red 289 was 54% by mass.

(Preparation salt product (A-13E))

By the following procedure, C.I. (A-13E) comprising Acid Red 289 and dilauryldimethylammonium chloride (molecular weight of the cation portion is 382) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. After the solution was heated to 70 to 90 캜, dilauryldimethylammonium chloride was added dropwise thereto. The dilauryldimethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of the dilauryldimethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes in order to sufficiently react. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-13E) which is a product salt product of Acid Red 289 and dilauryldimethylammonium chloride. C.I.H in the salt formation product (A-13E). The content of effective dye component derived from Acid Red 289 was 63% by mass.

(Preparation salt product (A-14E))

By the following procedure, C.I. (A-14E) comprising Acid Red 289 and tristearyl monomethylammonium chloride (molecular weight of the cation portion was 788) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and trisuteryl monomethylammonium chloride was added dropwise thereto. Tristearyl monomethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of tristearyl monomethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-14E) which is a product salt product of Acid Red 289 and tristearyl monomethylammonium chloride. A mixture of C.I. The content of effective dye component derived from Acid Red 289 was 45% by mass.

(Preparation salt product (A-15E))

By the following procedure, C.I. (A-15E) comprising Acid Red 52 and distearyldimethylammonium chloride (Cotamin D86P) (molecular weight of the cation portion is 550) was prepared. By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. To thereby dissolve the acid red 52, and this solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-15E) which is a product salt of the salt of Acid Red 52 with distearyldimethylammonium chloride. To a solution of C.I. The content of the effective coloring matter component derived from the Acid Red 52 was 50 mass%.

(Salt formation product (A-16E))

By the following procedure, C.I. (A-16E) comprising Acid Red 87 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 87 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-16E) which is a product salt product of Acid Red 87 and distearyldimethylammonium chloride. A mixture of C.I. The content of effective dye component derived from Acid Red 87 was 55% by mass.

(Preparation salt product (A-17E))

By the following procedure, C.I. (A-17E) comprising Acid Red 92 and trilaurylbenzyl ammonium chloride (molecular weight of the cation part is 612) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 92 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and trilaurylbenzylammonium chloride was added dropwise thereto. Trilaurylbenzylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of trilaurylbenzylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes in order to sufficiently react. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-17E) which is a product salt product of Acid Red 92 with trilauryl benzyl ammonium chloride. A solution of C.I. The content of the effective dye component derived from the Acid Red 92 was 57% by mass.

(Preparation salt product (A-18E))

By the following procedure, C.I. (A-18E) comprising Acid Red 388 and distearyldimethylammonium chloride (Kotamine D86P) (molecular weight of the cation portion was 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 388 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and to this was added drop wise Cotamin D86P. Cotamin D86P may be used as an aqueous solution. After completion of dropwise addition of the cocammin D86P, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-18E) which is a product salt product of Acid Red 388 and distearyldimethylammonium chloride. A mixture of C.I. The content of effective dye component derived from Acid Red 388 was 51 mass%.

(Preparation salt product (A-19E))

By the following procedure, C.I. (A-19E) comprising Acid Red 289 and dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride (Arquad 2HT-75) (molecular weight of the cation part is 438 to 550).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. After heating the solution to 70 to 90 캜, Arquad 2HT-75 was added dropwise to the solution. Arquad 2HT-75 may be used as an aqueous solution. After completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. To give a crude product (A-19E) which is the product of the salt formation of Acid Red 289 with dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride. A solution of C.I. The content of effective dye component derived from Acid Red 289 was 57% by mass.

(Preparation salt product (A-20E))

By the following procedure, C.I. (A-20E) comprising Acid Red 52 and dimethyl ammonium chloride (Arquad 2HT-75 having a molecular weight of 438 to 550 in the cation portion) having dialkyl (the number of the alkyl groups of 14 to 18).

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. To thereby dissolve the acid red 52, and this solution was sufficiently stirred. After heating the solution to 70 to 90 캜, Arquad 2HT-75 was added dropwise to the solution. Arquad 2HT-75 may be used as an aqueous solution. After completion of the dropwise addition of Arquad 2HT-75, the solution was stirred at 70 to 90 ° C for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-20E) which is a product salt of the salt of an acid red 52 with dialkyl (alkyl group having 14 to 18 carbon atoms) dimethyl ammonium chloride. A solution of C.I. The content of the effective coloring matter component derived from the Acid Red 52 was 53 mass%.

(Preparation salt product (A-21E))

By the following procedure, C.I. (A-21E) comprising Acid Red 289 and monolauryltrimethylammonium chloride (molecular weight of the cation part is 228) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and monolauryltrimethylammonium chloride was added dropwise thereto. Monolauryl trimethyl ammonium chloride may be used as an aqueous solution. After completion of dropwise addition of monolauryltrimethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes for sufficient reaction. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-21E) which was a product salt of the salt of Acid Red 289 with monolauryltrimethylammonium chloride. A solution of C.I. The content of effective dye component derived from Acid Red 289 was 74% by mass.

(Preparation salt product (A-22E))

By the following procedure, C.I. (A-22E) comprising Acid Red 289 and tetraethylammonium chloride (the molecular weight of the cation portion was 122) was prepared.

By mass of sodium hydroxide solution in 7 to 15 mol% sodium hydroxide solution. Acid Red 289 was dissolved and the solution was sufficiently stirred. This solution was heated to 70 to 90 占 폚, and tetraethylammonium chloride was added dropwise thereto. Tetraethylammonium chloride may be used as an aqueous solution. After completion of dropwise addition of tetraethylammonium chloride, this solution was stirred at 70 to 90 占 폚 for 60 minutes. At the end point of the reaction, the reaction liquid was dropped to the filter paper, and the time point at which the permeation was eliminated was determined. That is, it was judged that the crude product was obtained when the impregnation was eliminated. After cooling to room temperature with stirring, the mixture was subjected to suction filtration and further washed with water. After washing with water, moisture was removed from the salt formation product remaining on the filter paper using a drier, and C.I. (A-22E) which is a product salt product of Acid Red 289 and tetraethylammonium chloride. To a solution of C.I. The content of the effective coloring matter component derived from the Acid Red 289 was 84% by mass.

&Lt; Method for producing xanthan family compound >

(Xanthene compounds (C-1E) and (C-2E))

(C-1E) and (C-2E) were prepared in the same manner as described for the xanthene compounds (C-1A) and (C-2A).

&Lt; Production method of pigment dispersion >

(Preparation of Blue Pigment Dispersion (DP-1E)

The following mixture was stirred to homogeneity, and zirconia beads having a diameter of 0.5 mm were used and subjected to dispersion treatment for 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co.). Thereafter, the dispersion was filtered with a filter of 5.0 mu m to obtain a pigment dispersion (DP-1E).

Blue Fine Pigment 1E (CI Pigment Blue 15: 6): 11.0 parts

Acrylic resin solution 1E: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts

Resin type dispersant ("EFKA4300" manufactured by Chiba Japan): 1.0 part

(Preparation of Blue Pigment Dispersions (DP-2E) and (DP-3E)) [

Pigment dispersions (DP-2E) and (DP-3E) were prepared in the same manner as the pigment dispersion (DP-1E) except that the pigments were changed as shown in Table 26.

&Lt; Preparation method of resin solution containing salt formation product >

(Preparation of a salt solution-containing resin solution (DA-1E)

The following mixture was stirred to homogeneity and then filtered through a 5.0 탆 filter to obtain a resin solution (DA-1E) containing the salt formation product.

Preparation salt product (A-1E): 11.0 parts

Acrylic resin solution 1E: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

(Preparation of Formulation Product-Containing Resin Solutions (DA-2E) to (DA-11E) and Xanthene Compound-Containing Resin Solutions (DC-1E) and (DC-2E)

Containing resin solution (DA-1E) was obtained in the same manner as in the above-described formation product containing resin solution (DA-1E) except that the reaction product (A-1E) was changed to the reaction product (A) (DA-2E) to (DA-11E) and a xanthene-based compound-containing resin solution (DC-1E) and (DC-2E) were prepared. Table 27 shows the contents of the coloring matters. The dye content A indicates the content (mass%) of the effective dye component in the salt formation product (A) or the xanthene-based compound. The coloring matter content B represents the content (mass%) of the effective coloring matter component in the coloring agent-containing resin solution.

* 1 Dye content component content A: Content of effective dye component (% by weight) of the crude product (A) or xanthene-

* 2 Content of coloring matter component B: Content of effective coloring matter component (% by weight) in resin solution containing coloring agent

[Example 1E]

(Resist material (R-1E))

A resist material was prepared using the pigment dispersion thus obtained and the aqueous solution containing the salt formation product and the like, and the evaluation was carried out. First, a method of preparing a resist agent will be described.

The following mixture was stirred so as to be homogeneous, and then filtered through a filter of 1.0 mu m to obtain an alkali development type resist material (R-1E).

Salt solution containing resin solution (DA-1E): 21.0 parts

Pigment dispersion (DP-1E): 39.0 parts

Acrylic resin solution 1E: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

[Examples 2E to 25E and Comparative Examples 1E to 3E]

(Resist materials R-2E to R-28E)

(R-2E) to (R-2E) were prepared in the same manner as in the resist material (R-1E) except that the colorant-containing resin solution and the pigment dispersion and the blending amounts thereof were changed as shown in Table 28. [ -28E).

[Examples 26E to 31E]

(Resist materials (R-29E) to (R-34E))

(R-29E) and (R-30E) were prepared in the same manner as in the resist material (R-5E) except that the acrylic resin solution 1E was changed to acrylic resin solutions 2E, 3E and 4E. R-31E). (R-32E), (R-33E) and (R-33E) were prepared in the same manner as the resist material (R-10E) except that the acrylic resin solution 1E was changed to the acrylic resin solutions 2E, 3E and 4E. (R-34E).

(Evaluation of resist material)

A coating film was formed from the resist materials (R-1E) to (R-34E), and the color reproducibility and the amount of foreign matters were examined for each of these coating films by the following methods.

(Resist Evaluation Method)

The resist material was coated on the transparent substrate by a spin coater. The resist material was applied in such a thickness that the transmittance of the colored layer to light having a wavelength of 570 nm became 3%. The coating film was dried at 80 DEG C for 30 minutes using a hot air oven, and the film thickness and the spectral transmittance of the obtained colored layer were measured. The spectral transmittance was measured using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Kogaku Co., Ltd.). Then, the transmittance was added every 5 nm from 400 nm to 480 nm to obtain a value T ₁ . The transmittance was measured in the same manner for the transparent substrate on which the colored layer was not formed, and the transmittance was added every 5 nm from 400 nm to 480 nm to obtain the value T ₂ . Then, based on the ratio T ₁ / T ₂ between the values T ₁ and T ₂ , both sides of color reproduction were determined. The results are shown in Table 29.

In Table 29, the meanings of the symbols described in the column of &quot; color reproduction &quot; are as follows.

?: T ₁ / T ₂ is 0.765 or more

X: T ₁ / T ₂ is less than 0.765

(Method of foreign matter test on coated film)

The above resist material was evaluated for ease of occurrence of coating irregularity caused by foreign matter. Specifically, first, a resist material was applied on a transparent substrate so that the dry film thickness was about 2.5 占 퐉, and the entire surface of the coated film was exposed with ultraviolet rays. Thereafter, this was heated in an oven at 230 DEG C for 20 minutes and then cooled to obtain an evaluation substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was 500 times and observed in the transmission mode. Then, for any five visual fields, the number of identifiable particles was counted, and the total number of particles was obtained. The results are shown in Table 29.

In Table 29, the meanings of the symbols described in the column of &quot; foreign matter on the coating film &quot; are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

When the total number of particles is less than 20, coating irregularities caused by foreign matters hardly occur. When the total number of particles is 20 or more and less than 100, there are many foreign matters, but there is no problem in use. When the total number of particles is 100 or more, coating unevenness due to foreign matter occurs.

Resist materials (R-1E) to (R-25E) and (R-29E) to (R-34E) used in Examples 1E to 31E contain a blue pigment and a salt formation product (A). On the other hand, the resist material (R-26E) according to Comparative Example 1E contains a copper phthalocyanine pigment and a dioxazine-based pigment. Comparing these, the coloring layers obtained from the resist materials R-1E to R-25E and R-29E to R-34E were compared with the coloring layers obtained from the resist material R-26E , Good transmittance characteristics were exhibited, and color reproduction was excellent. Further, as can be seen from the results of Examples 26E to 31E, the use of an active energy ray curable resin having an ethylene bond was used to reduce foreign matters on the coating film.

The colored layers obtained from the resist materials (R-27E) and (R-28E) exhibited good transmittance characteristics, but a large amount of foreign matter was generated.

○ The sixth sun

The sixth aspect is a color filter for an organic EL display suitably used for a color display using a white light emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as &quot; organic EL element &quot;), And a color display provided with an organic EL element. Also, &quot; white &quot; includes pseudo-white.

As a color display using a color filter, for example, (i) a backlight as a light source, a liquid crystal layer as an optical shutter, and a color filter having a color adjustment function (a color conversion function, a color separation function, (Ii) an organic EL device including a combination of a white light source composed of one or more organic EL elements and a color filter having a color adjustment function (color conversion function, color separation function, color correction function, etc.) Display.

Liquid crystal displays are generally known as low power consumption. However, in a liquid crystal display, the backlight unit continues to emit light in the same manner as in white display, even in black display. That is, the liquid crystal display consumes energy unnecessarily.

In the organic EL display, a light source is provided for each pixel, and ON / OFF of each light source can be controlled by a TFT (thin film transistor) or the like. Therefore, the organic EL display can perform the black display by stopping the supply of the current to the light source. Further, in the organic EL display, the liquid crystal layer and the polarizing plate are unnecessary, and there is no loss of energy accompanying the absorption of light by the polarizing plate. Therefore, the organic EL display is advantageous in terms of power consumption. Further, in the organic EL display, the black display is performed by stopping the supply of the current to the light source, so that darker black can be displayed as compared with the liquid crystal display. Therefore, the organic EL display is also advantageous in terms of the contrast ratio.

Further, the organic EL display is described, for example, in Japanese Patent Application Laid-Open No. 2005-100921, and an organic EL display capable of displaying a color image has already been sold.

The organic EL display capable of displaying a color image has a structure in which an organic EL element that emits red light, an organic EL element that emits green light, and an organic EL element that emits blue light are arranged. In the production of such an organic EL display, a pattern of a light emitting layer of an organic EL element which emits red light, a pattern of a light emitting layer of an organic EL element which emits green light, a pattern of a light emitting layer of an organic EL element which emits blue light, It is necessary to form a pattern of Therefore, such an organic EL display is complicated in structure and manufacturing process, and requires high-precision mask alignment in its manufacture. Therefore, it is difficult to manufacture the organic EL display at a low cost, high definition and large screen. In order to solve these problems, it has been proposed that the light-emitting layer is a white light-emitting layer to be described later, and the white light-emitting layer and the color filter are combined (JP-A-2004-47469, JP-A-2008-518400, JP-A-07-220871 ).

In a display capable of displaying a color image, color reproduction is important. For example, the color reproduction of a color liquid crystal display is determined by the color of the light emitted by the red, green and blue filter segments, and is evaluated by the following method. That is, the chromaticity coordinates (xR, yR), (xG, yG) and (xB, yB) of the red, green and blue filter segments are plotted on the x, y chromaticity diagrams and the area of the triangle enclosed by these three points is I ask. In addition, the chromaticity coordinates (0.67, 0.33), (0.21, 0.71) and (0.14, 0.08) x, y chromaticity coordinates of the three primary colors determined by the National Television System Committee (NTSC) Find the area of the triangle enclosed by the point. The color reproduction is evaluated based on the ratio of the area of the former to the area of the latter (unit:%, hereinafter abbreviated as NTSC ratio). In general, the value is preferably 40 to 100% for a notebook type computer, 50 to 100% for a monitor of a desktop type computer, 70 to 100% for a liquid crystal television, .

As a backlight of a liquid crystal display, for example, a backlight including a cold cathode tube as a light source and a backlight including a light emitting diode or an organic EL element made of an inorganic material as a light source, for example, a backlight including two peaks There is a pseudo-white backlight of the wavelength type or a three-wavelength type backlight whose luminescence spectrum has three peaks. Regarding the backlight including a light source other than the organic EL element, a bright line spectrum is designed in terms of the display performance of the liquid crystal display, specifically, the color reproducibility achieved by matching with the color filter, and the durability of the backlight.

An organic EL element used as a white light source in an organic EL display and a backlight can be, for example, a two-wavelength type light source having an emission spectrum of two peaks, a three-wavelength type light source having an emission spectrum of three peaks, The spectrum is a light source having many peaks. The white light source includes a white light emitting layer composed of a mixture containing a plurality of organic EL materials emitting light of different colors or a laminate of a plurality of light emitting layers emitting light of different colors as a white light emitting layer.

The organic EL element as a white light source has a different luminescence spectrum from a cold cathode tube used as a white light source and a light emitting diode made of an inorganic material. For example, the emission spectrum of a cold cathode tube as a white light source or a light emitting diode made of an inorganic material has a peak at or near 420 to 430 nm. On the other hand, the emission spectrum of the organic EL device as a white light source generally has no peak at or near 420 to 430 nm due to the characteristics of the material, and has a peak at about 460 nm. The emission spectrum of the organic EL element as a white light source has a broad peak as a whole compared with the emission spectrum of a cold cathode tube as a white light source or a light emitting diode made of an inorganic material. Specifically, the former has a higher emission intensity within a wavelength range from about 460 nm to about 500 nm, as compared with the latter. For these reasons, the color filter currently used can not be used as it is for a display including the organic EL element as a white light source. For this reason, it is necessary to select and develop a color filter material that exhibits optimal color and transmittance characteristics when combined with an organic EL device as a white light source.

For example, in order to increase the NTSC ratio in an organic EL display including a white light source and an organic EL display including a color filter, it is necessary to increase the color purity of each filter segment. However, if the color purity is increased, the utilization efficiency of the light emitted by the light source (corresponding to the brightness Y) is lowered, and the power consumption is increased.

In the case of a product mainly driven by a battery such as a portable device, since the power consumption is important, the NTSC ratio of a color liquid crystal display mounted on such a product has been low as 30 to 50%. However, nowadays, since there is a lot of opportunity to view pictures or videos on a portable device, there is a growing demand for a NTSC ratio in a display of a portable device. Therefore, in the organic EL display, it is desired that the color purity and the brightness Y of each filter segment are high.

Conventionally, a blue filter segment of an organic EL display is often formed of a coloring composition containing a phthalocyanine pigment excellent in resistance and color tone. It is known that the phthalocyanine pigment has various central metals such as copper, zinc, nickel, cobalt and aluminum. Among them, copper phthalocyanine is widely used because it can display a clear color, and compounds other than copper phthalocyanine such as metal phthalocyanine, zinc phthalocyanine and cobalt phthalocyanine are put to practical use. Phthalocyanine pigments have different crystal forms such as?,?,?, And?, And all have excellent properties such as high saturation and high coloring power. Therefore, they are suitable as colorants for color filters. In the conventional color filter, these copper phthalocyanine pigments are mixed with the dioxazine-based pigment C.I. Pigment Violet 23 or the like, a wide color display area could be achieved.

It has also been conventionally employed to use a coloring agent in combination with a pigment and a dye in a color filter. For example, it has been proposed to use a copper phthalocyanine pigment and an oil-soluble dye, a disperse dye or an alkaline dye as a blue filter segment (see, for example, JP-A-11-242109 and JP-A-2001-124915 ).

It has also been proposed to use a xanthene dye in a color filter, and it is also known that a color filter excellent in heat resistance can be obtained by using it with acydodamine (CI Acid Red 52) and a polyimide resin or a photosensitive acrylic resin (See, for example, Japanese Patent Application Laid-Open No. 6-59114).

However, even when these techniques are applied to the above organic EL display, it is difficult to achieve sufficiently high color purity and brightness.

The color filter according to the sixth aspect comprises a green filter segment, a red filter segment, and a blue filter segment. The blue filter segment is formed from a blue coloring composition containing a binder resin and a colorant. The colorant contains a blue pigment and a salt formation product. The salt formation product is formed from a compound having a cationic group and a xanthene acid dye.

The blue filter segment of the color filter according to the sixth aspect is capable of having a high brightness and a wide color reproduction area. Since the dye is in the form of a salt formation product, the blue filter segment of the color filter according to the present embodiment can have excellent performance in terms of heat resistance, light resistance and solvent resistance.

Further, by combining this blue filter segment and the red and green filter segments each including a specific pigment, a color filter capable of achieving a high white lightness Y and NTSC ratio is obtained. Therefore, by combining this color filter with a light emitting device including a white light emitting organic EL element as a light source, a color display having high brightness Y of white and high NTSC ratio can be obtained.

When the content of the blue pigment is 100 parts by mass, particularly excellent performance can be achieved when the amount of the effective dye component in the salt formation product is in the range of 5 to 150 parts by mass.

<< Blue coloring composition >>

The blue coloring composition used in this embodiment contains a salt formation product (A) obtained by reacting a compound (a) having a cationic group with a xanthene acid dye, a blue pigment, and a binder resin. The blue coloring composition may contain an organic solvent, a dispersing aid, a photopolymerizable compound, a photopolymerization initiator, and other additives as described in detail below, if necessary.

In this embodiment, the colorant is composed of the pigment component and the salt formation product (A).

<Preparation salt product (A)>

The salt formation product (A) is a salt formation product obtained by reacting a compound (a) having a cationic group with a xanthene acid dye.

(The compound (a) having a cationic group)

The compound having a cationic group is not particularly limited as long as it is a compound having at least one onium base. The compound having an onium base is preferably an ammonium salt compound, an iodonium salt compound, a sulfonium salt compound, a diazonium salt compound, or a phosphonium salt compound. Among them, preferred compounds having a cationic group are a resin (a1) having a cationic group in the side chain or a quaternary ammonium compound (a2) represented by the following general formula (24).

The general formula (24)

[In the formula (24), R ₁ to R ₄ each independently represents an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion.]

The preferred form of the compound (a) having a cationic group is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more, in the entire wavelength range of 400 to 700 nm which is a visible light region. That is, it is preferable that the compound (A) having a cationic group does not inhibit the color development of the dye component and does not cause color change.

[Resin (a1) having cationic group in side chain]

As the resin (a1) having a cationic group in the side chain, the resin (a1) having a cationic group in the side chain of the fourth aspect may be used in the same manner.

[Quaternary ammonium compound (a2) represented by the general formula (24)] [

As the quaternary ammonium compound (a2) represented by the general formula (24), the quaternary ammonium compound of the first aspect can be used in the same manner.

The general formula (24)

[In the formula (24), R ₁ to R ₄ each independently represents an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion.]

Among them, the quaternary ammonium compound (a2) represented by the general formula (24) is a compound wherein R ₁ to R ₄ each independently represent an alkyl group having 1 to 20 carbon atoms or a benzyl group, 20 &lt; / RTI &gt;

(Xanthene acid dye)

As the xanthene acid dye for obtaining the salt formation product (A), the xanthene acid dye of the first embodiment can be used in the same manner.

(Condensation treatment)

[Salt Formation of Resin (a1) Having Cationic Group in Side Chain and Xanthan Acidic Dye]

(A1) having a cationic group in a side chain and a salt-forming product comprising a xanthene acid dye can be obtained by the same method as described in the paragraph of "(salt formation)" in the fourth aspect. The ratio of the resin (a1) having a cationic group in the side chain to the xanthene acid dye is preferably the same as that described in the fifth aspect.

[Formation of salt of quaternary ammonium compound (a2) with xanthene acid dye]

The crude product of the xanthene acid dye and the quaternary ammonium compound (a2) can be obtained by the same method as described in the first aspect.

(The content of the effective coloring matter component contained in the salt formation product (A)

The content of the effective coloring matter component derived from the xanthine acid dye in the salt formation product (A) is the same as in the fourth aspect.

<Blue pigment>

As the blue pigment constituting the colorant, the phthalocyanine-based pigment is used in the same manner as in the first embodiment. As the phthalocyanine-based pigment, it is preferable to use a copper phthalocyanine blue pigment.

Among these, C.I. Pigment Blue 15: 6 is preferably used.

(Fineness of pigment)

The blue pigment used in the color filter of this embodiment and other pigments optionally used can be minified by performing a salt milling treatment in the same manner as in the first aspect. The primary particle diameter of the pigment is preferably 20 nm or more from the viewpoint of dispersibility into the colorant carrier. From the viewpoint of forming a filter segment having a high contrast ratio, it is preferable that the thickness is 100 nm or less. A particularly preferable range is 25 to 85 nm.

The diameter of the primary particles of the pigment is determined from an electron microscope photograph of the pigment by a TEM (transmission electron microscope). Specifically, first, pigment particles are sampled on a grid mesh to prepare a sample for TEM observation. Subsequently, this sample is observed by TEM, and the minor axis diameter and the major axis diameter of the primary particle are measured for each of 100 or more pigment particles. And, the average of them is set as the primary particle diameter of the pigment particle.

The salt formation product (A) is preferably used in an amount of 1 to 800 parts by mass, more preferably 5 to 400 parts by mass, per 100 parts by mass of the blue pigment. If the addition amount of the salt formation product (A) is less than 1 part by mass, reproducible chromaticity regions become narrow. When the added amount exceeds 800 parts by mass, the color is changed.

Considering the color structure, the content of the effective coloring matter component in the salt formation product (A) is preferably in the range of 1 to 400 parts by mass with respect to 100 parts by mass of the blue pigment. It is more preferable that the mass of the effective dye component in the salt formation product (A) is in the range of 5 to 150 parts by mass with respect to 100 parts by mass of the blue pigment.

Particularly, as a xanthene acid dye, C.I. Acid Red 289 or C.I. The salt formation product (A) using the acid red 52 is excellent in solvent solubility and achieves excellent heat resistance, light resistance and solvent resistance when used in combination with a blue pigment. The reason why the salt formation product (A) is used in combination with the blue pigment to achieve good performance is that the salt formation product (A) is adsorbed on the blue pigment while dissolved or dispersed in the solvent.

&Lt; Other coloring agents >

In the blue coloring composition of the present embodiment, other organic pigments may be added to the blue coloring composition in addition to the components of the coloring agent, as long as they do not interfere with obtaining the effect, for coloring purposes, as in the first embodiment.

<Binder Resin>

The binder resin is to disperse the coloring agent, in particular the crude salt product, or to dye or penetrate the crude product. Examples of the binder resin include a thermoplastic resin and a thermosetting resin, and the "resin" of the first aspect can be used in the same manner.

<Organic solvents>

In the blue coloring composition of this embodiment, the coloring agent is dispersed or dissolved sufficiently in the coloring agent carrier, and the filter segment is formed on the substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 占 퐉 Solvents may be included for ease of handling.

As the organic solvent, the solvent of the first or fifth aspect may be used in the same manner.

<Dispersion>

In the color filter of the present embodiment, a coloring agent containing a coloring agent (A) obtained by reacting a blue pigment and a cationic group-containing compound (a) with a xanthene acid dye is mixed with a binder resin and an organic solvent A coloring composition prepared by a treatment using various dispersion means such as 3 roll mill, 2 roll mill, sand mill, kneader, and stirrer may be used in the colorant carrier to be used, preferably with a dispersion aid such as a pigment derivative. In the color filter of this embodiment, a coloring composition prepared by dispersing a blue pigment, a salt formation product (A) and other coloring agents in a coloring agent carrier, and then mixing them may be used.

(Dispersion auxiliary)

When the colorant is dispersed in the colorant carrier, as in the fourth aspect, a dispersion aid such as a pigment derivative, a resinous dispersant, and a surfactant can be appropriately used.

As the pigment derivative, the pigment derivative of the fourth aspect may be used in the same manner.

It is preferable to use a basic compound of copper phthalocyanine having a basic substituent group introduced into the phthalocyanine pigment as the dye derivative. As the basic compound of copper phthalocyanine, an amine compound of copper phthalocyanine, for example, an ammonium salt compound of copper phthalocyanine sulfonate, a copper phthalocyanine tertiary amine, or a copper phthalocyanine sulfonic acid amide compound is preferable.

By using a basic compound of copper phthalocyanine, particularly an amine compound of copper phthalocyanine, a blue filter segment having high brightness and high contrast ratio can be realized. This is because the basic compound of copper phthalocyanine suppresses the generation of fluorescence derived from the xanthene acid dye while improving the dispersibility of the blue pigment. Particularly, it is significant that the crude product (A) having a xanthene acidic dye in the blue coloring composition coexists with a basic compound of copper phthalocyanine.

The basic compounds of copper phthalocyanine may be used alone, but two or more kinds of them may be used in combination. The basic compound of copper phthalocyanine is preferably used in an amount of 0.01 to 200 parts by mass based on 100 parts by mass of the total amount of the blue pigment, more preferably 1 to 100 parts by mass.

The ratio of the mass of the basic compound of copper phthalocyanine to the mass of the salt formation product (A) (basic compound of copper phthalocyanine / salt formation product (A)) is preferably 0.3 to 1.5. In this case, fluorescence generated from the salt formation product (A) can be suppressed while improving dispersion of the blue pigment, and as a result, a blue coloring composition capable of realizing a color filter with high brightness and a high contrast ratio can be obtained.

If it is less than 0.3, the contrast is lowered because of suppression of fluorescence and insufficient dispersibility of the amine compound of copper phthalocyanine. If it exceeds 1.5, the color characteristics are affected and it may become prominent. A more preferable mass ratio is 0.4 to 1.2, and a most preferable mass ratio is 0.5 to 1.1.

As the resinous dispersant, the resinous dispersant of the first aspect may be used in the same manner.

As the surfactant, the surfactant of the first aspect may be used in the same manner.

When the resinous dispersant and / or surfactant is added, the amount thereof is preferably in the range of 0.1 to 55 parts by mass, more preferably in the range of 0.1 to 45 parts by mass, based on 100 parts by mass of the total amount of the colorant desirable. When the blending amount is less than 0.1 part by mass, the effect of the resin type dispersant and / or the surfactant is hardly obtained. If the blending amount is more than 55 parts by mass, the dispersion may be affected by an excessive dispersing agent.

&Lt; Photopolymerizable compound >

The blue coloring composition used in the production of the color filter of the present invention may further be added with a photopolymerizable compound and / or a photopolymerization initiator and used as a photosensitive blue coloring composition for a color filter. As the photopolymerizable compound, the photopolymerizable compound of the first aspect can be used in the same manner.

<Photopolymerization initiator>

In this embodiment, the photopolymerization initiator of the first aspect can be used in the same manner.

<Increase / decrease>

The blue coloring composition used in the production of the present color filter can further contain a sensitizer in the same manner as in the first embodiment.

<Leveling agent>

In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the blue coloring composition in the same manner as in the first aspect.

<Curing agent, hardening accelerator>

The blue coloring composition used in this embodiment may contain a curing agent, a curing accelerator, and the like as necessary in order to assist curing of the thermosetting resin, as in the first embodiment.

&Lt; Other additive components >

The blue coloring composition used in this embodiment may contain a storage stabilizer in the same manner as in the first embodiment in order to keep the viscosity of the composition substantially constant over a long period of time. Further, in order to improve the adhesion with the transparent substrate, the adhesion improving agent such as a silane coupling agent may be contained in the same manner as in the first aspect.

<Antioxidant>

In order to increase the transmittance of the coating film, the coloring composition used in this embodiment preferably contains an antioxidant in the same manner as in the first aspect.

<Removal of Coarse Particles>

From the blue coloring composition used in the production of the color filter of this embodiment, coarse particles of 5 mu m or more, preferably coarse particles of 1 mu m or more, more preferably 0.5 It is preferable to remove coarse particles of 탆 or more and dust mixed therein.

<< Color Filter >>

The color filter according to this aspect includes, for example, a plurality of filter segments that are different in absorption spectrum, and are typically arranged in a regular fashion. One form of the color filter has at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter according to the present embodiment, for example, the blue filter segment is formed from the above-mentioned coloring composition for a color filter.

The red filter segment can be formed by using a common red coloring composition including a red pigment and a pigment carrier in the same manner as in the first embodiment. In the red coloring composition, an orange color pigment and / or a yellow color pigment may be used together in the same manner as in the first aspect.

Considering the matching between the transmission spectrum of the red filter segment and the emission spectrum of the white organic EL device, from the viewpoint of realizing a high brightness and a wide color display region, the red filter segment has a C.I. Pigment Red, 177 and C.I. Pigment Red 179. It is preferable that the red pigment contains at least one kind of red pigment selected from the group consisting of red pigment. The reason why it is preferable to use these pigments in the red filter segment is that the high coloring power of these pigments is effective for the development of a wide color display region.

The green filter segment can be formed by using a conventional green coloring composition including a green pigment and a pigment carrier in the same manner as in the first embodiment. In the green coloring composition, yellow pigments can be used in combination as in the first embodiment.

Considering the matching between the transmission spectrum of the green filter segment and the emission spectrum of the white organic EL device, from the viewpoint of realizing a high brightness and a wide color display region, the green filter segment has a C.I. Pigment Green 7 and C.I. At least one kind of green pigment selected from the group consisting of C.I. Pigment Yellow 139, C.I. Pigment Yellow 150 and C.I. Pigment Yellow 185, which is a yellow pigment. In the green filter segment, the reason why the combination of these pigments is preferable is that the high coloring power of these pigments is effective for the development of a wide color display region.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass, and alkali-free alumino-borosilicate glass, or resin plates such as polycarbonate, polymethyl methacrylate and polyethylene terephthalate are used. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for liquid crystal driving after paneling.

<Manufacturing Method of Color Filter>

The color filter of the present embodiment can be manufactured by, for example, a printing method, a photolithography method, an electrodeposition method, a transfer method, an ink-jet method, or the like. The coloring composition used in this embodiment can be applied to any additional method.

According to the printing method, patterned filter segments can be formed only by repeating printing and drying of the coloring composition prepared as a printing ink. Therefore, the printing method is inexpensive and excellent in mass productivity. Further, by the development of the printing technique, it is possible to form a fine pattern having high dimensional accuracy and smoothness by printing.

The ink used for printing preferably has a composition that does not dry and solidify on a printing plate or blanket. In the printing method, it is also important to control the fluidity of the ink on the printing press. The flowability of the ink can be controlled by adjusting the ink viscosity using a dispersing agent or extender pigment.

According to the photolithography, the color filter can be manufactured with higher precision as compared with the printing method.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developing type or alkali-developing type coloring resist is applied onto the transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating , And the dry film thickness is, for example, in the range of 0.2 to 5 mu m. The coating film is dried as required and is passed through a mask having a predetermined pattern provided in contact or noncontact state with the coating film, and the coating film is exposed to ultraviolet rays. Thereafter, the coating film is immersed in a solvent or an alkaline developing solution, or a solvent or an alkaline developing solution is sprayed onto the coating film to remove the uncured portion from the coating film. Thus, a thin film pattern corresponding to a filter segment of a certain color is obtained. The same operations as those described above are repeated to form a thin film pattern corresponding to the remaining filter segments, except that a coloring composition for filter segments of different colors is used. Thereafter, these thin film patterns are fired as necessary to obtain a color filter. The firing may be performed every time a thin film pattern is formed.

At the time of development, for example, aqueous solutions such as sodium carbonate and sodium hydroxide are used as the alkali developing solution. Organic alkali such as dimethylbenzylamine and triethanolamine may be used. A defoaming agent or a surfactant may be added to the developer.

In order to enhance ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is coated on the colored resist film formed by applying and drying the colored resist, Thereafter, ultraviolet ray exposure may be performed. A coating film composed of a water-soluble or alkali-soluble resin prevents the polymerization in the colored resist film from being inhibited by oxygen.

In manufacturing the color filter using the electrodeposition method, a substrate provided with a transparent conductive film on one main surface is prepared, and the filter segment is formed by using the transparent conductive film as an electrode and electrophoretically moving the colloidal particles on the transparent conductive film.

In manufacturing the color filter using the transfer method, filter segments are previously formed on the main surface in front of the transfer base sheet having one separable main surface, and the filter segments are transferred from the transfer base sheet to the substrate.

On the transparent substrate, a black matrix, which is a light-shielding pattern, may be formed before the filter segments are formed. As the black matrix, for example, a metal film such as a chromium film, a multilayer film such as a chromium / chromium oxide film, an inorganic compound film such as a titanium nitride film, or a resin film in which a light shielding material is dispersed in a resin is used.

An active matrix circuit including a thin film transistor (TFT) may be formed on the transparent substrate before a color filter is formed. Other layers such as an overcoat film and a transparent conductive film may be further formed on the color filter, if necessary. By forming the filter segments on the TFT substrate, the aperture ratio of the display panel can be increased and the brightness can be improved.

<< Color display >>

The color display in the present embodiment is a color display comprising a base salt product (A) obtained by reacting a cationic group-containing compound (a) with a xanthate acid dye and a blue color filter formed of a blue coloring composition comprising a colorant containing a blue pigment and a binder resin A color filter having a segment, and a white light-emitting organic EL element (hereinafter referred to as an organic EL element) as a light source.

(Organic EL element (white light-emitting organic EL element))

The organic EL device used in this embodiment has a peak wavelength in which the luminescence spectrum has two or more peak values in the wavelength range of 400 nm to 700 nm and within the wavelength range of 430 to 485 nm and within the wavelength range of 580 to 620 nm, the ratio I2 / I1 of the light emission intensity I2 at the wavelength? 2 to the light emission intensity I1 at the wavelength? 1 is preferably 0.4 to 0.9, more preferably 0.5 to 0.8, and particularly preferably 0.5 To 0.7.

It is preferable that the luminescence spectrum of the organic EL element has a maximum value or a shoulder of light emission intensity within a wavelength range of 530 to 650 nm.

The reason why the peak wavelength? 1 is within the wavelength range of 430 nm to 485 nm is that the color display including the color filter is advantageous for displaying blue with high color reproduction. The peak wavelength? 1 is more preferably in the range of 430 nm to 475 nm.

By using the organic EL element and the color filter satisfying these configurations, a color display with a wide color reproduction area, high definition and high contrast ratio can be obtained.

The organic EL element is constituted by an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode. Here, the single-layer type organic EL element refers to a device including only a light emitting layer between an anode and a cathode. On the other hand, for the purpose of facilitating the injection of holes and electrons into the light-emitting layer and facilitating the recombination of holes and electrons in the light-emitting layer, in addition to the light-emitting layer, the multilayer organic EL element includes a hole injection layer, , A hole blocking layer, and an electron injection layer. Typical device configurations of the multilayer organic EL device include (1) anode / hole injecting layer / light emitting layer / cathode, (2) anode / hole injecting layer / hole transporting layer / light emitting layer / cathode, (3) anode / (5) anode / hole injecting layer / light emitting layer / hole blocking layer / electron injecting layer / cathode, (6) electron injection layer / cathode, (4) anode / hole injecting layer / hole transporting layer / light emitting layer / (7) anode / light emitting layer / hole blocking layer / electron injecting layer / cathode, and (8) anode / light emitting layer / electron injecting layer / electron injecting layer / electron injecting layer / electron injecting layer / positive hole injecting layer / hole transporting layer / light emitting layer / A cathode, and the like. However, the structure of the organic EL device used in this embodiment is not limited to these.

Each of the above organic layers may have a laminated structure of two or more layers. In this case, a plurality of layers may be repeatedly laminated. As such an example, for the purpose of improving light extraction efficiency, an element configuration called "multi-photon emission" for multilayering a part of the layers of the above-described multilayer organic EL element has been proposed recently. As an example of such an element structure, in an organic EL device composed of a glass substrate / anode / hole transporting layer / electron transporting light emitting layer / electron injecting layer / charge generating layer / light emitting unit / cathode, a plurality of parts of the charge generating layer and the light emitting unit are laminated Configuration.

Hereinafter, materials usable for these layers will be specifically exemplified. However, the materials usable in this embodiment are not limited to these.

As a material usable for the hole injection layer, a phthalocyanine-based compound is preferable. Examples of the phthalocyanine compound include copper phthalocyanine (CuPc) and vanadyl phthalocyanine (VOPC). In addition, a material obtained by chemically doping a conductive polymer compound can also be used. Examples of such a material include a material doped with polystyrene sulfonic acid (PSS) in polyethylene dioxythiophene (PEDOT). It is also possible to use polyaniline (PANI). A thin film made of an inorganic semiconductor such as molybdenum oxide (MoO _x ), vanadium oxide (VO _x ) and nickel oxide (NiO _x ), or an ultra-thin film made of an inorganic insulator such as aluminum oxide (Al ₂ O ₃ ) Can be used. Further, it is also possible to use 4,4 ', 4 "-tris (N, N-diphenyl-amino) -triphenylamine (TDATA), 4,4'N'-diphenyl-1,1'-biphenyl-4,4'-diamine (TPD), 4,4'- Bis (N, N-diethylamino) -biphenyl (? -NTPD) and 4,4'-bis [N- -Tolyl) amino) phenyl-N-phenylamino] biphenyl (DNTPD) can also be used. A substance exhibiting acceptor properties may be added to the aromatic amine compound. For example, it is possible to add 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), which is an acceptor to VOPc, It is also possible to use MoO _x added as a susceptor.

As the material of the hole transporting layer, aromatic amine-based compounds are suitable. For example, TDATA, MTDATA, TPD, alpha -NPD and DNTPD described in the hole injecting material can be used.

As the material of the electron transport layer, for example, tris (8-quinolinolato) aluminum (Alq _3), tris (4-methyl-8-quinolinolato) aluminum (Almq _3), bis (10-hydroxy Benzo [h] -quinolinato) beryllium (BeBq ₂ ), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (BAlq), bis [2- ) Benzooxazolato] zinc (Zn (BOX) ₂ ), and bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (Zn (BTZ) ₂ ). In addition, it is also possible to use 1,3- bis [5- (p-tert-butylphenyl) -1,3,4-oxadiazole (PBD) (4-tert-butylphenyl) -4-phenyl-5- (4-methylphenyl) -1,3,4-oxadiazol- Biphenyl) -1,2,4-triazole (TAZ) and 3- (4-tert-butylphenyl) -4- , And 4-triazole (p-EtTAZ), 2,2 ', 2 "- (1,3,5-benzenetriyl) tris [1-phenyl-1H- benzoimidazole] (TPBI) , Or phenanthroline derivatives such as benzophenanthroline (BPhen) and basocuproin (BCP) may be used.

Examples of the electron injection layer material, e.g., the aforementioned _{Alq 3, Almq 3, BeBq 2} , BAlq, Zn (BOX) 2, Zn (BTZ) 2, PBD, OXD-7, TAZ, p-EtTAZ, TPBI, An electron transporting material such as BPhen and BCP can be used. As the electron injection layer, an ultra-thin film of an insulator, for example, an alkali metal halide such as LiF and CsF, an alkaline earth halide such as CaF ₂ , or an alkali metal oxide such as Li ₂ O may be used. Alkali metal complexes such as lithium acetylacetonate (Li (acac)) and 8-quinolinolato-lithium (Liq) may also be used. To these electron injecting materials, a substance showing donor property may be added thereto. As the donor, for example, an alkali metal, an alkaline earth metal or a rare earth metal may be used. For example, a donor lithium may be added to BCP or a donor lithium may be added to Alq ₃ .

As the material of the hole blocking layer, a material which is excellent in film forming property and can prevent the holes passing through the light emitting layer from reaching the electron injection layer is used. Examples of such materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolato) aluminum, bis (2-methyl-8-hydroxyquinolinato) , And nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP).

The light emitting layer emitting white light is not particularly limited, and for example, the following can be used. That is, as described in European Patent No. 0390551, a white light-emitting organic EL element which optimizes the energy level of each layer and emits light by tunnel injection; Similarly, the white light-emitting organic EL device described in the embodiment of Japanese Unexamined Patent Publication No. 3-230584 as an element using tunnel injection; A white light-emitting organic EL element including a light-emitting layer of a two-layer structure, as disclosed in Japanese Unexamined Patent Application Publication No. 2-220390 and Japanese Unexamined Patent Publication No. 2-216790; A white light-emitting organic EL device in which a light-emitting layer is divided into a plurality of portions and the light-emitting layer is made of a material having a different light emission wavelength, as disclosed in Japanese Patent Laid-Open No. 4-51491; A white light-emitting organic EL device in which a blue luminescent layer (fluorescent peak of 380 to 480 nm) and a green luminescent layer (480 to 580 nm) are laminated and further contains a red phosphor, as disclosed in Japanese Unexamined Patent Application Publication No. 6-207170; And a laminate of a blue luminescent layer and a green luminescent layer as described in Japanese Unexamined Patent Publication No. 7-142169, the blue luminescent layer is made of a blue luminescent material, optionally doped with a blue fluorescent dye, Emitting layer of a white light-emitting organic EL device made of a green light-emitting material, a part of which is doped with a red fluorescent dye, and a part of which is doped with a green fluorescent dye arbitrarily.

As the light emitting material, conventionally known materials can be used as the light emitting material. Hereinafter, blue, green, and compounds which are suitably used for light emission of orange or red are exemplified. In addition, the light emitting material is not limited to those specifically illustrated below.

Blue light emission is obtained by using, for example, perylene, 2,5,8,11-tetra-t-butyl perylene (TBP), and 9,10-diphenylanthracene derivatives as a guest material. Blue luminescence is a styrylarylene derivative such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPVBi), 9,10-di-2-naphthylanthracene , And 10-bis (2-naphthyl) -2-tert-butyl anthracene (t-BuDNA). A polymer such as poly (9,9-dioctylfluorene) may also be used.

A more preferable specific example is shown in Table 30.

Examples of green light emission include coumarin-based colorants such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinato iridium (FIrpic) Phenylpyridinate) acetylacetonatoyl lithium (Ir (ppy) (acac)) as a guest material. Also, green light emission, tris (8-hydroxy-Quinoline) aluminum (Alq _3), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) gallium chloro (Ga (mq) ₂ Cl ) Or the like. A polymer such as poly (p-phenylene vinylene) may also be used.

A more preferable specific example is shown in Table 31.

The coloring or red luminescence is, for example, selected from the group consisting of rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6- Pyridine (DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -2-methyl- (2-phenylquinolinato) acetylacetonatoimidazole (Ir (thp) 2 (acac)) and bis [2- (2-thienyl) pyridinyl] (Ir (pq) (acac)) as a guest material. The colored or red luminescence can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (Znq ₂ ) or bis [2-cinnamoyl-8-quinolinolato] zinc (Znsq ₂ ). A polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may also be used.

A more preferable specific example is shown in Table 32.

As the material of the anode of the organic EL device, a metal, an alloy, an electrically conductive compound or a mixture thereof having a large work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au and conductive materials such as CuI, ITO, SNO ₂ and ZNO. The anode is obtained by forming a thin film made of these electrode materials by a vapor deposition method, a sputtering method or the like. When the light from the light emitting layer is taken out from the anode, it is preferable that the anode has a transmittance with respect to light from the light emitting layer of more than 10%. The sheet resistance of the anode is preferably several hundreds? / Cm ² or less. The film thickness of the anode varies depending on the material, but is usually selected in the range of 10 nm to 1 탆, preferably in the range of 10 to 200 nm.

As the material of the cathode of the organic EL device, a metal, an alloy, an electrically conductive compound or a mixture thereof having a small work function (4 eV or less) is used. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium-silver alloy, aluminum / aluminum oxide, aluminum-lithium alloy, indium and rare earth metals. The negative electrode is obtained by forming a thin film composed of these electrode materials by a method such as vapor deposition or sputtering. When the light from the light emitting layer is taken out from the cathode, it is preferable that the cathode has a transmittance with respect to the light emitted from light emission greater than 10%. The sheet resistance of the negative electrode is preferably several hundreds? / Cm ² or less. The film thickness of the negative electrode is usually in the range of 10 nm to 1 mu m, preferably in the range of 50 to 200 nm.

The organic EL device may be formed by forming the anode, the light emitting layer, the hole injecting layer and, if necessary, the electron injecting layer, if necessary, and finally forming the cathode using the above materials and methods. Further, the organic EL elements may be manufactured by reversing the order of stacking.

The organic EL device is fabricated, for example, on a light-transmitting substrate. The translucent substrate is a substrate for supporting the organic EL device, and preferably has a transmittance of 50% or more, more preferably 90% or more in the entire visible region of 400 to 700 nm. It is also preferable to use a smooth substrate.

The translucent substrate has mechanical and thermal strength, and is not particularly limited as long as it is transparent. As the translucent substrate, for example, a glass plate or a synthetic resin plate is suitably used. Examples of the glass plate include soda lime glass, glass containing barium and strontium, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, or quartz. Examples of the synthetic resin plate include a plate made of a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, or a polysulfone resin.

Each layer of the organic EL device can be formed by a wet film formation method such as vacuum deposition, electron beam irradiation, sputtering, dry film formation such as plasma and ion plating, spin coating, dipping, flow coating and ink jet method, (LITI) method described in Japanese Patent Application Laid-Open No. 2002-534782 or ST Lee, et al., Proceedings of SID'02, p. 784 (2002) , Printing (offset printing, flexographic printing, gravure printing, screen printing), or ink jetting.

It is preferable that the organic layer is a minute-subtracting film in particular. Here, the term "minute-subtracting film" is a thin film formed by depositing a compound in a gaseous state, or a film formed by solidifying a compound in a solution state or a liquid state. Usually, this molecular deposition film can be distinguished from a thin film (molecular accumulation film) formed by the LB method by a difference in cohesive structure or higher order structure, and a functional difference resulting therefrom. Also, as disclosed in Japanese Patent Laid-Open No. 57-51781, an organic layer can be formed by dissolving a binder and a material compound of a resin in a solvent to form a solution, and then making the solution into a thin film by a spin coating method or the like. The film thickness of each layer is not particularly limited. However, if the film thickness is excessively large, a large applied voltage is required to obtain a constant light output, resulting in deterioration of efficiency. Conversely, if the film thickness is too thin, pinholes, It is difficult to obtain sufficient light emission luminance. Therefore, the film thickness of each layer is preferably in the range of 1 nm to 1 占 퐉, and more preferably in the range of 10 nm to 0.2 占 퐉.

Further, in order to improve the stability of the organic EL element against temperature, humidity, atmosphere, etc., a protective layer may be formed on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when covering or sealing the entire element, a photo-curable resin which is cured by light is suitably used.

The current applied to the organic EL element is usually a direct current, but a pulse current or alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within a range that does not destroy the device. However, considering the power consumption and lifetime of the device, it is desirable to efficiently emit light with as little electric energy as possible.

The driving method of the organic EL element can be driven not only by the passive matrix method but also by the active matrix method. The method of extracting light from the organic EL element may be a bottom emitter for extracting light from the anode side, or a top emitter for extracting light from the cathode side. These methods and techniques are described in Kidao Junji, &quot; All of Organic EL, &quot; published by Nihon Zetsugyo Publishing Co. (published in 2003).

In this embodiment, a color filter is used to enable color display, for example, full color display. In the color filter system, white light emitted by a white light-emitting organic EL element is incident on a color filter to extract light of three primary colors. In addition to these three primary colors, if a part of white light is taken out as it is for light emission, the luminous efficiency of the entire device can be increased.

The organic EL device may employ a microcavity structure. The organic EL element has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light may cause multiple interferences between the anode and the cathode. By appropriately selecting the optical characteristics of the positive electrode and the negative electrode, for example, the reflectance and the transmittance, and the film thickness of the organic layer sandwiched between them, it is possible to cause an interference which is stronger and stronger with respect to light having a predetermined wavelength. This makes it possible to improve the emission chromaticity. The mechanism of this multiple interference effect is described in AM-LCD Digest of Technical Papers, OD-2, pp. 77-80 (2002) by J. Yamada et al.

An organic EL display including a color filter is obtained, for example, by forming a color filter layer on a substrate and placing the organic EL device thereon. In this display, when a predetermined circuit including a TFT is provided in each pixel, it is possible to realize a particularly high contrast ratio.

(Example F)

Hereinafter, this embodiment will be described on the basis of embodiments, but the present invention is not limited thereto. In the examples, &quot; part &quot; and &quot;% &quot; indicate &quot; part by mass &quot; and &quot;% by mass &quot;, respectively. The weight average molecular weight (Mw) of the acrylic resin is a weight average molecular weight (Mw) in terms of polystyrene. The weight average molecular weight (Mw) was measured by a gel permeation chromatographic apparatus (Hoso Corporation, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh Corporation). THF was used as a developing solvent.

First, an organic EL device, an acrylic resin solution, a finely divided pigment, a resin (a) having a cationic group in its side chain, a salt formation product (A), a xanthene compound, a pigment dispersion, , A xanthene-based compound-containing resin solution, a blue resist material, a red resist material, and a green resist material will be described below, and the examples and comparative examples of this embodiment will be described in detail.

&Lt; Example of production of organic EL device &

An example of production of an organic EL device to be used as a white light source is shown below. In the production example of the organic EL device, unless otherwise stated, the mixing ratio represents the mass ratio. The deposition (vacuum deposition) was performed under a vacuum of 10 ^-6 Torr under conditions without temperature control such as substrate heating and cooling. In the evaluation of the luminescence characteristics of the device, the characteristics of the organic EL device having the electrode area of 2 mm x 2 mm were measured.

(Production of organic EL device EL-1)

The cleaned glass plate with the ITO electrode was treated with oxygen plasma for about 1 minute and then 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl To obtain a hole injection layer having a film thickness of 150 nm. Compound (R-2) and compound (R-3) shown in Table 3 were co-deposited on the hole injection layer at a composition ratio of 100: 2 to form a first light emitting layer having a thickness of 10 nm. Subsequently, the compound (B-1) and the compound (B-4) shown in Table 1 were co-deposited on the first light emitting layer at a composition ratio of 100: 3 to form a second light emitting layer having a thickness of 20 nm. Subsequently, α-NPD was vacuum-deposited on the second light-emitting layer to a thickness of 5 nm and the compound (G-3) shown in Table 2 was vacuum-deposited to a thickness of 20 nm to form a third light-emitting layer. Thus, a light emitting layer comprising the first to third light emitting layers was obtained.

Next, a tris (8-hydroxynolin) aluminum complex was vacuum-deposited on the light-emitting layer to form an electron injection layer having a thickness of 35 nm. Subsequently, lithium fluoride was vacuum deposited on the electron injecting layer to a thickness of 1 nm, and aluminum was further deposited to a thickness of 200 nm to form an electrode. Thus, the organic EL device EL-1 was obtained.

In order to protect the organic EL element EL-1 from the surrounding environment, hermetic sealing was performed in a dry glow box filled with pure nitrogen. A direct current voltage of 5 V of 5 V was applied between the electrodes to emit light to the organic EL device EL-1 to obtain white light emission having an emission luminance of 950 cd / m ² , a maximum emission luminance of 55000 cd / m ² and an emission efficiency of 3.9 lm / W . Fig. 2 shows the emission spectrum thereof.

(Production of organic EL element EL-2)

N-phenylamino] biphenyl (? -NPD) was added to a glass plate with an ITO electrode treated in the same manner as in the production of the organic EL device (EL-1) Was vacuum-deposited to form a hole injection layer having a film thickness of 50 nm. Compound (R-2) and compound (R-3) shown in Table 3 were co-deposited on the hole injection layer at a composition ratio of 100: 0.5 to form a first light emitting layer having a thickness of 20 nm. Subsequently, the compound (B-3) and the compound (B-4) shown in Table 1 were co-deposited on the first light emitting layer at a composition ratio of 100: 2 to form a second light emitting layer having a thickness of 40 nm. Subsequently, a tris (8-hydroxynolin) aluminum complex was vacuum-deposited on the second light-emitting layer to form a third light-emitting layer having a thickness of 30 nm. Thus, a light emitting layer comprising the first to third light emitting layers was obtained.

Next, on this luminescent layer, α-NPD was vacuum-deposited to a thickness of 5 nm, and a tris (8-hydroxynolin) aluminum complex was vacuum-deposited to prepare an electron injecting layer having a thickness of 20 nm. Subsequently, lithium fluoride was vapor-deposited on the electron injecting layer to a thickness of 1 nm, and aluminum was vapor-deposited to a thickness of 300 nm to form an electrode. Thus, the organic EL device EL-2 was obtained.

In order to protect the organic EL element EL-2 from the surrounding environment, hermetic sealing was performed in a dry glow box filled with pure nitrogen. A direct current voltage of 5 V of 5 V was applied between the electrodes to emit the organic EL element EL-2. As a result, white light emission having an emission luminance of 1,500 cd / m ² , a maximum emission luminance of 68,000 cd / m ² and an emission efficiency of 3.11 m / lost. 3 shows the emission spectrum thereof.

For each of the organic EL elements EL-1 and EL-2, the peak wavelength lambda 1 in the wavelength range of 430 nm to 485 nm and the peak wavelength (in the wavelength range of 580 nm to 620 nm) of the luminescence spectrum lt; 2 &gt; The ratio I2 / I1 of the light emission intensity I2 at the wavelength? 2 to the light emission intensity I1 at the wavelength? 1 is also shown in Table 33.

&Lt; Process for producing acrylic resin solution >

(Preparation of acrylic resin solution 1F)

An acrylic resin solution 1F was prepared in the same manner as described for the acrylic resin solution 1A.

(Preparation of blue fine pigment)

The phthalocyanine-based blue pigment C.I. 200 parts of Pigment Blue 15: 6 ("LIONOL BLUE ES" available from Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (INOUE SEKUSHO Co., Ltd.) Over 6 hours. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day and one night to obtain 190 parts of a blue fine pigment.

(Preparation of purple fine pigment)

CI. &Lt; / RTI &gt; 200 parts of Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink and Chemicals, Inc.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were charged into a stainless steel first gallon kneader (Inoue Seisakusho) Kneaded over time. Next, this kneaded material was charged into 8 liters of hot water, and stirred for 2 hours while heating at 80 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying at 85 ° C for one day and one night, to obtain 190 parts of a purple fine pigment.

(Preparation of red fine pigment 1F)

The red pigment C.I. , 152 parts of Pigment Red 177 ("CROMOPHTAL RED A2B" manufactured by Chiba Japan), 8 parts of the dye derivative A-2 shown in Table 5, 1600 parts of sodium chloride and 190 parts of diethylene glycol (manufactured by Tokyo Kasei Co., Ltd.) (Manufactured by Inoue Chemicals Co., Ltd.) and kneaded at 60 占 폚 for 10 hours. Next, the mixture was poured into about 5 liters of hot water, and stirred with a high-speed mixer for about one hour while heating at about 70 DEG C to obtain a slurry. Thereafter, filtration and washing were performed to remove sodium chloride and diethylene glycol, and dried at 80 DEG C for 24 hours to obtain 156 parts of a red fine pigment 1F.

(Preparation of red fine pigment 2F)

The red pigment C.I. 500 parts of Pigment Red 179 pigment ("Paliogen Maroon L-3920" manufactured by BASF Japan Ltd.), 500 parts of sodium chloride and 250 parts of diethylene glycol were charged into a stainless steel first gallon kneader (INOUE CERASCO) And kneaded at 120 DEG C for 8 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, and the mixture was dried at 80 DEG C for one day and one night to obtain 490 parts of red fine pigment 2F.

(Preparation of Green Fine Pigment 1F)

The phthalocyanine-based green pigment C.I. 500 parts of Pigment Green 7 ("Lionol Green YS-07" manufactured by Toyo Ink and Chemicals, Inc.), 500 parts of sodium chloride and 250 parts of diethylene glycol were charged into a stainless steel first gallon kneader (INOUE CERASCO) Lt; 0 &gt; C for 4 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to obtain 490 parts of a green fine pigment 1F.

(Production of green fine pigment 2F)

The phthalocyanine-based green pigment C.I. 500 parts of Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink and Chemicals, Ltd.), 500 parts of sodium chloride and 250 parts of diethylene glycol were charged into a stainless steel first gallon kneader (INOUE CERASCO Co., Ltd.) Kneaded over 4 hours. Next, this kneaded product was charged into 5 liters of warm water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. Filtration and washing were repeated to remove sodium chloride and diethylene glycol, followed by drying overnight at 80 ° C to obtain 490 parts of a green fine pigment 2F.

(Preparation of Yellow Fine Pigment 1F)

The phthalocyanine-based green pigment C.I. Pigment Green 7 was mixed with an isoindoline yellow pigment C.I. 490 parts of yellow fine pigment 1F was obtained in the same manner as in the preparation of the green fine pigment 1F, except that Pigment Yellow 150 ("E-4GN" manufactured by LANXESS) was changed to a kneading time of 4 hours to 8 hours.

(Preparation of yellow fine pigment 2F)

The phthalocyanine-based green pigment C.I. Pigment Green 7 was mixed with an isoindolinone yellow pigment C.I. Except that Pigment Yellow 139 ("Irgafour Yellow 2R-CF" manufactured by Chiba Japan Co., Ltd.) was changed to a kneading time of 4 hours to 8 hours, 490 parts of yellow A fine pigment 2F was obtained.

(Preparation of yellow fine pigment 3F)

The phthalocyanine-based green pigment C.I. Pigment Green 7 was mixed with an isoindoline yellow pigment C.I. 490 parts of yellow fine pigment 3F was obtained in the same manner as in the preparation of the green fine pigment 1F, except that Pigment Yellow 185 ("Palliogen Yellow D1155" manufactured by BASF) was changed to a kneading time of 4 hours to 8 hours .

<Method for preparing resin (a1) having cationic group in side chain>

(Preparation of Resin 1F Having a Cationic Group in the Side Chain)

A resin 1F having a cationic group in the side chain was prepared by the same method as described for the resin 1D.

(Preparation of Resin 2F Having a Cationic Group in the Side Chain)

Resin 2F having a cationic group in its side chain was prepared by the same method as described for Resin 2D.

(Preparation of Resin 3F Having a Cationic Group in the Side Chain)

Resin 3F having a cationic group in the side chain was prepared by the same method as described for Resin 3D.

(Preparation of Resin 4F Having a Cationic Group in the Side Chain)

Resin 4F having a cationic group in the side chain was prepared by the same method as described for Resin 4D.

(Preparation of Resin 5F Having a Cationic Group in the Side Chain)

Resin 5F having a cationic group in the side chain was prepared by the same method as described for Resin 5D.

&Lt; Preparation of crude salt product >

(Preparation salt product (A-1F))

The salt formation product (A-1F) was prepared in the same manner as described for the salt formation product (A-1D).

(Preparation salt product (A-2F))

The salt formation product (A-2F) was prepared in the same manner as described for the salt formation product (A-2D).

(Preparation salt product (A-3F))

The salt formation product (A-3F) was prepared in the same manner as described for the salt formation product (A-3D).

(Preparation salt product (A-4F))

The salt formation product (A-4F) was prepared in the same manner as described for the salt formation product (A-4D).

(Preparation salt product (A-5F))

The salt formation product (A-5F) was prepared in the same manner as described for the salt formation product (A-5D).

(Preparation salt product (A-6F))

The salt formation product (A-6F) was prepared in the same manner as described for the salt formation product (A-6D).

(Preparation salt product (A-7F))

(A-7F) was prepared in the same manner as described for the salt formation product (A-7D).

(Preparation salt product (A-8F))

The salt formation product (A-8F) was prepared in the same manner as described for the salt formation product (A-8D).

(Preparation salt product (A-9F))

The salt formation product (A-9F) was prepared in the same manner as described for the salt formation product (A-9D).

(Preparation salt product (A-10F))

The salt formation product (A-10F) was prepared in the same manner as described for the salt formation product (A-10D).

(Preparation salt product (A-11F))

The salt formation product (A-11F) was prepared in the same manner as described for the salt formation product (A-11D).

(Preparation salt product (A-12F))

The salt formation product (A-12F) was prepared in the same manner as described for the salt formation product (A-19E).

&Lt; Method for producing xanthan family compound >

(Xanthene compounds (C-1F) and (C-2F))

(C-1F) and (C-2F) were prepared in the same manner as described for the xanthene compounds (C-1A) and (C-2A).

&Lt; Production method of pigment dispersion >

(Pigment Dispersions (BP-1F), (BP-2F), (VP-1F) ), (YP-2F) and (YP-3F)

The mixture of the pigment derivative, pigment, acrylic resin solution 1F, resin type dispersant ("EFKA4300" manufactured by Chiba Japan Co., Ltd.) and organic solvent described in Table 34 was stirred so as to be uniform as shown in Table 35, and then 1 mm diameter zirconia Beads were used and dispersing treatment was performed over 5 hours by Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan). Thereafter, 30.0 parts of propylene glycol monomethyl ether acetate (hereinafter may be abbreviated as PGMAc) was added to the dispersion, and this was filtered with a 5 mu m filter to obtain a pigment dispersion.

&Lt; Preparation method of resin solution containing salt formation product >

(Preparation of a salt solution-containing resin solution (DA-1F)

The following mixture was stirred so as to be homogeneous, and then filtered through a 5.0 탆 filter to obtain a resin solution (DA-1F) containing the salt formation product.

Preparation salt product (A-1F): 11.0 parts

Acrylic resin solution 1F: 40.0 parts

Cyclohexanone: 49.0 parts

(Preparation of Decomposition Product-Containing Resin Solution (DA-2F) to (DA-12F), Xanthene Compound-Containing Resin Solution (DC-1F), (DC-

Containing resin solution (DA-1F) was obtained in the same manner as in the above-described formation product containing resin solution (DA-1F) except that the crude product (A-1F) (DA-2F) to (DA-12F) and a xanthene-based compound-containing resin solution (DC-1F) and (DC-2F) were prepared. Table 36 shows the contents of the pigment components. The dye content A indicates the content (mass%) of the effective dye component in the salt formation product (A) or the xanthene-based compound. The dye content B represents the content (mass%) of the effective dye component in the colorant-containing resin solution.

* 1 Dye content component content A: Content of effective dye component (% by weight) of the crude product (A) or xanthene-

* 2 Content of coloring matter component B: Content of effective coloring matter component (% by weight) in resin solution containing coloring agent

&Lt; Preparation of blue resist material (blue coloring composition) (BR-1F) to (BR-21F)

(Blue resist material BR-1F)

The following mixture was stirred to homogeneity, and then filtered through a filter of 1.0 mu m to obtain an alkali developing type blue resist material (BR-1F).

Salt solution containing resin solution (DA-1F): 21.0 parts

Pigment dispersion (BP-1F): 39.0 parts

Acrylic resin solution 1F: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Blue resist materials BR-2F to BR-21F)

(BR-2F) to (BL-2F) were prepared in the same manner as in the case of the blue resist material (BR-1F) except that the colorant- containing resin solution and the pigment dispersion and the blending amounts thereof were changed as shown in Table 37. [ (BR-21F).

(Characteristics of resist material)

A coating film was formed from the resist materials BR-1F to BR-21F, and the chromaticity and the amount of foreign matter of these coating films were examined by the following methods.

(Fabrication of blue filter segments)

A black matrix as a light-shielding pattern was formed on a glass substrate, and then a blue resist material shown in Table 38 was applied using a spin coater. The blue resist material is a resist material having a film thickness such that the chromaticity x and y are the values shown in Table 38 when combined with the blue filter segment obtained from the blue resist material and the organic EL device EL-1 or EL-2 Respectively. This coating film was irradiated with ultraviolet rays at an exposure dose of 150 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was applied to a spraying phenomenon to remove unexposed portions, followed by washing with ion-exchanged water. Here, 0.15 part by mass of sodium carbonate, 0.05 part by mass of sodium hydrogencarbonate, 0.1 part by mass of an anionic surfactant ("Perillax NBL" manufactured by Kao Corporation) and 99.7 parts by mass of water were used as a developing solution. Thereafter, this substrate was heated at 230 캜 for 20 minutes to obtain a blue filter segment.

(Chromaticity)

Table 38 shows the chromaticities when the blue filter segments are combined with the organic EL element EL-1 or EL-2.

(Method of foreign matter test on coated film)

The blue resist material was coated on the transparent substrate so that the dry film thickness was about 2.5 mu m, and the entire surface of the coated film was exposed with ultraviolet rays. Thereafter, this was heated in an oven at 230 DEG C for 20 minutes and then cooled to obtain an evaluation substrate. Subsequently, the surface of each test substrate was observed using a metal microscope &quot; BX60 &quot; manufactured by Olympus Systems. Here, the magnification was 500 times and observed in the transmission mode. Then, for any five visual fields, the number of identifiable particles was counted, and the total number of particles was obtained. Table 38 shows the results.

In Table 38, the meanings of the symbols described in the column of "foreign matter on the coating film" are as follows.

?: Total number of particles less than 5

○: The total number of particles is 5 or more and less than 20

?: The total number of particles is 20 or more and less than 100

X: the total number of particles is 100 or more

The blue filter segment formed from the blue resist material BR-1F to BR-14F had a higher brightness Y than the blue filter segment formed from the blue resist material BR-15F. With respect to the blue filter segments formed of the blue resist materials BR-16F and BR-17F, the brightness Y was high, but the foreign matter on the coating film was extremely large. Also for the organic EL element EL-2 having a different luminescence spectrum from the organic EL element EL-1, the blue filter segment formed of the resist material containing the blue pigment and the salt formation product (A) Respectively.

&Lt; Production method of red resist material (RR-1F) and green resist materials (GR-1F) to (GR-4F)

(Preparation of red resist material (RR-1F)

The following mixture was stirred to homogeneity, and then filtered with a filter of 1.0 mu m to obtain an alkali development type resist material (RR-1F).

Pigment dispersion (RP-1F): 30.0 parts

Pigment dispersion (RP-2F): 30.0 parts

Acrylic resin solution 1F: 11.0 parts

Trimethylolpropane triacrylate ("NK Ester ATMPT" manufactured by Shin Nakamura Kagaku): 4.2 parts

Photopolymerization initiator ("Irgacure-907" manufactured by Chiba Japan): 1.2 parts

("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 part

Propylene glycol monomethyl ether acetate (PGMAC): 23.2 parts

(Preparation of green resist materials GR-1F to GR-4F)

Green resist materials (GR-1F) to (GR-4F) were obtained in the same manner as in the case of the red resist material (RR-1F) except that the colorant dispersion and the blending amount thereof were changed as shown in Table 39.

[Example 1F]

(Fabrication of color filter CF-1F)

A black matrix as a light-shielding pattern was formed on a glass substrate, and then a red resist material (RR-1F) was applied using a spin coater. When the filter segments obtained from the resist material and the organic EL element EL-1 were combined, the red resist material (RR-1F) was applied in such a thickness that the chromaticity x and y became the values shown in Table 41 . This coating film was irradiated with ultraviolet rays at an exposure dose of 300 mJ / cm &lt; ² &gt; through a photomask using an ultra-high pressure mercury lamp. Subsequently, this coating film was subjected to a spraying development using an alkali developing solution composed of an aqueous solution of sodium carbonate of 0.2 mass% to remove unexposed portions, followed by washing with ion-exchanged water. Further, this substrate was heated at 230 占 폚 for 20 minutes to obtain a red filter segment.

Next, a green resist material (GR-1F) was coated on the glass substrate using a spin coater. The green resist material GR-1F was applied in such a film thickness that the chromaticity x and y became the values shown in Table 41 when the filter segment obtained from the resist material and the organic EL element EL-1 were combined . Thereafter, the same exposure, development, cleaning, and heating as those described for the red filter segment were performed to obtain a green filter segment.

Then, a blue resist material (BR-1F) was coated on the glass substrate using a spin coater. The blue resist material BR-1F was applied in such a film thickness that the chromaticity x and y became the values shown in Table 41 when the filter segment obtained from this resist material and the organic EL element EL-1 were combined . Thereafter, the same exposure, development, cleaning, and heating as those described for the red filter segment were performed to obtain a blue filter segment.

Thus, a color filter CF-1F was obtained.

[Examples 2F to 19F and Comparative Examples 1F to 4F]

(Fabrication of color filters CF-2F to CF-23F)

(CF-2F) to (CF-19F) were prepared in the same manner as the color filter (CF-1F) except that the red, green and blue resist materials and the organic EL elements were changed as shown in Table 40 .

When red, green and blue resist materials and organic EL devices were changed as shown in Table 40 and the filter segments obtained from the respective resist materials were combined with the organic EL device EL-2, the chromaticities x and y Color filters CF-20F to CF-23F were produced in the same manner as in the case of the color filter CF-1F except that the color filters CF-1F and CF-2F were applied in the same thickness as shown in Table 41.

[Color evaluation of color filters]

The color filters prepared in Examples and Comparative Examples were combined with organic EL elements EL-1 and EL-2 as shown in Table 40. [ Then, the organic EL device was caused to emit light, and the color characteristic of the color filter was measured using a brown spectrophotometer ("OSP-SP100" manufactured by Olympus Kogaku Co., Ltd.). Table 41 shows the chromaticity coordinates (x, y), the NTSC ratio, and the brightness (Y value) in white display in the CIE colorimetric system of each filter segment.

Comparing Examples 1F to 16F with Comparative Example 1F shows that when a blue filter segment is formed from a coloring composition containing a blue pigment and a salt formation product (A), a blue filter segment is formed from a coloring composition containing a copper phthalocyanine pigment and a dioxazine- The brightness at the time of white display was high, the NTSC ratio was large, and the color reproducibility was good, as compared with the case where the segments were formed. In Comparative Examples 2F and 3F, the brightness at the time of white display was high, but a large number of foreign matters were generated as described above.

As can be seen from the results of Examples 17F to 19F and Comparative Example 4F, even when the organic EL device was changed from the element EL-1 to the element EL-2 having different luminescence spectra, Good performance could be achieved as compared with the case where the blue filter segment was formed from the coloring composition containing the component (A).

Claims (33)

Wherein the coloring agent comprises a blue pigment and a salt formation product, the salt formation product is formed from a compound having a cationic group and a xanthene acid dye, and the compound having a cationic group is a quaternary ammonium compound, An amine, and a resin having a cationic group in the side chain, wherein the amine is a primary amine having an alkyl group having 8 to 24 carbon atoms and an alkyl group having 8 to 22 carbon atoms or a benzyl group having 8 to 22 carbon atoms A secondary amine, and a tertiary amine. delete The blue coloring composition for a color filter according to claim 1, wherein the compound having a cationic group comprises a quaternary ammonium compound represented by the following general formula (1).
In general formula (1):

[In the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group. Y ^- represents an inorganic or organic anion.] The blue coloring composition for a color filter according to claim 3, wherein the molecular weight of the cation of the quaternary ammonium compound represented by the general formula (1) is in the range of 190 to 900. The compound according to claim 3, wherein, in the general formula (1), R ₁ to R ₄ each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two of R ₁ to R ₄ have a carbon atom number 5 to 20. &lt; / RTI &gt; The resin composition according to claim 1, wherein the compound having a cationic group includes a resin having a cationic group in the side chain, and the resin having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following formula (2) &Lt; / RTI &gt;
The general formula (2)

[In the general formula (2), R ⁵ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₆ to R ₈ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and two of R ₆ to R ₈ are bonded to each other to form a ring . Q represents an alkylene group, an arylene group, -CONH-R ₉ -, or -COO-R ₉ -, and R ₉ represents an alkylene group. Y- represents an inorganic or organic anion.] delete The blue coloring composition for a color filter according to claim 1, wherein the molecular weight of the amine is in the range of 129 to 591. delete The method according to claim 1, wherein the salt-forming product is prepared by mixing a resin having a cationic group in the side chain and the xanthate acidic dye in an aqueous solution, and reacting the counter anion of the resin having a cationic group in the side chain and the counter anion of the xanthate acid dye Wherein the compound is a compound obtained by removing a salt composed of a cation. The blue coloring composition for a color filter according to claim 1, wherein the blue pigment is a phthalocyanine pigment and / or a triarylmethane lake pigment. 12. The method according to claim 11, wherein the blue pigment comprises a phthalocyanine pigment, and the phthalocyanine pigment is C.I. Pigment Blue 15: 6. &Lt; / RTI &gt; [3] The method according to claim 1, wherein the xanthene acid dye is C.I. Wherein the red coloring composition is classified into an acid red and an acid red. 14. The composition of claim 13, wherein the xanthene acid dye is selected from the group consisting of C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, and C.I. Acid Red 388. The blue coloring composition for a color filter according to any one of claims 1 to 5, The colorant according to claim 1, wherein the colorant is selected from the group consisting of C.I. Pigment violet (23). &Lt; / RTI &gt; The blue coloring composition for a color filter according to claim 1, wherein the coloring agent further comprises a dioxazine-based pigment. The blue coloring composition for a color filter according to claim 1, further comprising an amine compound of copper phthalocyanine. 18. The blue coloring composition for a color filter according to claim 17, wherein the amine compound of copper phthalocyanine has a structure represented by general formula (4).
In general formula (4):
P-Lm
Wherein P is an m-valent copper phthalocyanine pigment residue, m is an integer of 1 to 4, and L is selected from the group represented by the general formula (5), (6), or (7) Lt; / RTI &gt;
The general formula (5)

In general formula (6):

(7): &lt; EMI ID =

[Among the general formulas (5) to (7)
X _{is, -SO 2 -, -CO-, -CH} 2 -, -CH 2 NHCOCH 2 -, -CH 2 NHSO 2 CH 2 -, or a direct bond,
Y ⁰ is -NH-, -O-, or a direct bond,
n is an integer of 1 to 10,
Y ¹ is -NH-, -NR ⁹ -Z-NR ¹⁰ -, or a direct bond,
R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group,
Z represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms.
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or R ¹ and R ² are combined to form a nitrogen, oxygen, or sulfur atom Further comprising a heterocyclic ring,
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms ,
R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms,
R ⁸ is a substituent represented by the general formula (5) or a substituent represented by the general formula (6)
Q represents a hydroxyl group, an alkoxyl group having 1 to 20 carbon atoms, a substituent represented by the general formula (5), or a substituent represented by the general formula (6). 18. The blue coloring composition for a color filter according to claim 17, wherein the mass ratio of the xanthene dye to the amine compound of the copper phthalocyanine is in the range of 0.3 to 1.5. 18. The blue coloring composition for a color filter according to claim 17, wherein the blue pigment is a copper phthalocyanine pigment. 18. The blue coloring composition for a color filter according to claim 17, wherein the xanthene dye is a rhodamine dye. The blue coloring composition for a color filter according to claim 1, wherein the amount of the effective coloring matter component in the preparation salt is in the range of 5 to 150 parts by mass when the content of the blue pigment is 100 parts by mass. The blue coloring composition for a color filter according to claim 1, further comprising a photopolymerizable compound and / or a photopolymerization initiator. The blue coloring composition for a color filter according to claim 1, further comprising an organic solvent containing propylene glycol monomethyl ether acetate as a main component. The coating film formed from the colored composition according to claim 1, wherein the coating film formed so as to have a spectral transmittance of 3% at a wavelength of 570 nm has a spectral transmittance of 50% within a range of 490 to 510 nm, and a spectral transmittance at a wavelength of 450 nm Or more and 85% or more, and a spectral transmittance of 11% or less at a wavelength of 540 nm. A green filter segment, a red filter segment, and a color filter having a blue filter segment formed from the blue coloring composition according to any one of claims 1, 3, 4, 5, 6, 8, filter. 27. The color filter according to claim 26, which is for a solid-state imaging device. 27. The color filter according to claim 26, which is for an organic EL display. The white light emitting organic EL device according to claim 28, wherein the emission spectrum has two or more maximum values within a wavelength range of 400 to 700 nm, peak wavelength λ ₁ and λ ₂ a having a wavelength λ emission intensity at ₂ I ₂ and the wavelength ratio I ₂ / I ₁ of the light-emitting intensity at λ ₁ I ₁ emits white light in the range of 0.4 to 0.9 represents the (XB, yB) in the CIE colorimetric system of the transmitted light emitted by the blue filter segment satisfies the relations represented by the inequalities xB? 0.160 and yB? 0.100, when the white light is incident on the blue filter segment Features a color filter. The white light emitting organic EL device according to claim 28, wherein the emission spectrum has two or more maximum values within a wavelength range of 400 to 700 nm, peak wavelength λ ₁ and λ ₂ a having a wavelength λ emission intensity at ₂ I ₂ and the wavelength ratio I ₂ / I ₁ of the light-emitting intensity at λ ₁ I ₁ emits white light in the range of 0.4 to 0.9 represents the (XR, yR), (xG, yG) and (xG, yG) in the CIE colorimetric system of the transmitted light emitted by the blue, green and red filter segments, respectively, (0.67, 0.33), (0.21, 0.71), and (0.14, 0.08), the area of the triangle is calculated by plotting a triangle with vertices Of 85% or more of the area of The color filter according to. 27. The method of claim 26, wherein the red filter segment is selected from the group consisting of C.I. Pigment Red 177 and C.I. Pigment Red &lt; RTI ID = 0.0 &gt; 179. &lt; / RTI &gt; 27. The method of claim 26, wherein the green filter segment is selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. At least one green pigment selected from the group consisting of Pigment Green 58 and C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185. The color filter according to claim 1, 26. A color display comprising the color filter according to claim 26 and a light emitting device including a white light emitting organic EL element as a light source.

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