JPH11302285A - Porphyrazine derivative, ink, color filter, liquid crystal panel, computer, and method of manufacturing color filter - Google Patents

Abstract

(57) [Problem] To provide a color filter having a blue pixel portion excellent in transparency, light resistance and heat resistance. SOLUTION: A blue pixel portion of a color filter is colored by combining a dye composed of a porphyrazine derivative having a nitrogen-containing aromatic ring and, if necessary, a pigment composed of a phthalocyanine derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blue pigment which can be suitably used for forming a color filter, an ink for ink-jet recording, a color filter of a color liquid crystal display used in a color television, a personal computer, etc. The present invention relates to a filter manufacturing method and a liquid crystal panel using such a color filter.

[0002]

2. Description of the Related Art A color filter is a valuable component of a color liquid crystal display. This filter has a large number of pixels consisting of three primary colors of red (R), green (G) and blue (B) repeatedly arranged on a transparent substrate. Has a structure. In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. However, cost reduction is required for further widespread use, and in particular, there is an increasing demand for cost reduction of color filters having high specific gravity in terms of cost. Conventionally, various color filter manufacturing methods have been attempted to satisfy the above requirements while satisfying the required characteristics of the color filters. Hereinafter, a typical method for manufacturing a color filter will be described.

The first method most frequently used is a dyeing method. The dyeing method uses a photosensitive material added to a water-soluble polymer material that is a material for dyeing and sensitized.
After patterning this into a desired shape on a transparent support by a photolithography process, the obtained pattern is immersed in a dye bath to obtain a colored pattern. This is repeated three times to form R, G, B color filters.

[0004] The second method which is most frequently used is a pigment dispersion method, which has recently been replaced by a dyeing method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and a monochromatic pattern is obtained by patterning the photosensitive resin layer. Further, by repeating this process three times, color filters of three colors of R, G, and B are formed.

A third method is an electrodeposition method. In this method, a transparent electrode is first patterned on a substrate. Next, it is immersed in an electrodeposition coating solution containing a pigment, a resin, an electrolyte solution, etc.
Electrodeposit the color. This process is repeated three times, and R, G, B
The color filter layer is formed by forming the color filter layer and finally baking the color filter layer.

As a fourth method, there is a printing method. In this method, a coating material in which a pigment is dispersed in a thermosetting resin is applied in three colors R, G, and B by repeated printing, and then the resin as a coloring layer is cured by heating to form a coloring layer. Is formed.

[0007] The above-described various methods still have many problems to be solved. For example, in each of the above-described methods, a protective layer is generally formed on a colored layer. Common to these methods is that R,
The same process is required three times to form G and B, which inevitably increases the cost. There is also a problem that the yield increases as the number of steps increases.
Furthermore, in the third method, since the pattern that can be formed is limited, it is difficult to apply the present technology to a TFT color. Furthermore, the fourth method has a drawback that resolution and smoothness are poor, and it is difficult to form a fine pitch pattern.

In order to improve these drawbacks, a method of manufacturing a color filter using an ink jet system has been proposed (JP-A-59-75205 and JP-A-63-75205).
-235901, JP-A-1-217302, JP-A-4-123005). In this method, a coloring liquid (hereinafter, ink) containing each of red (R), green (G), and blue (B) dyes is jetted from a nozzle onto a filter substrate, and the ink adheres to the filter substrate.
The filter is formed by drying to form pixels. According to this method, each of the R, G, and B colored layers can be formed at a time, and the ink can be attached to the pixel forming portion. The cost can be improved, and the cost can be reduced.

As a dye for forming a blue pixel, a phthalocyanine compound has conventionally been often used. The phthalocyanine compound has excellent properties such as light resistance and heat resistance due to its strong structure, is easy to synthesize, and has excellent optical properties such as an absorption coefficient and a transmittance.

[0010]

Attempts have been made to further improve the transmittance of the blue pixel portion in order to further enhance the performance of the color filter. There is a method of matching the wavelength at which the transmittance of the bright line and the blue pixel portion is maximized. For this purpose, JP-A-60-130715 and JP-A-7-253577 are used.
No. 6,086,045.

However, when a phthalocyanine compound is used as a main component dye of a blue pixel portion of a color filter,
The wavelength at which the transmittance of the blue pixel portion becomes maximum is on the longer wavelength side than the emission line peak of the three-wavelength tube, and is often inappropriate for obtaining such an improvement effect. Therefore, it has high solvent solubility, high extinction coefficient, and when used as a color filter dye, it has excellent light resistance and heat resistance, and the wavelength showing the maximum transmittance matches the three-wavelength tube, that is, it is transparent in the three-wavelength tube. There is a demand for a dye suitable for forming a blue pixel portion having high performance.

On the other hand, it is preferable that the ink used for manufacturing a color filter by discharging the ink by an ink jet system satisfy the following characteristics at a higher level, for example. a) High transparency of the color filter colored portion (pixel). b) Suppression of the change over time of the color filter colored portion (pixel) area (hereinafter referred to as “smearing”). c) High adhesion of the color filter colored portion (pixel). d) High light resistance of the color filter colored portion (pixel). e) High ejection stability when ejected by the inkjet recording method.

That is, one of the major differences between the method for producing a color filter using the ink jet method and the conventional method for producing a color filter is that, for example, as shown in FIG. That is, the ink is selectively adhered only to the portion, and thereafter, a solvent or a dispersion medium (water, an organic solvent, or the like) in the ink is evaporated to form a pixel.
However, according to the studies by the present inventors, depending on the ink used, in the process of drying the ink 24 adhered on the substrate on the substrate, when a dye is used as a coloring material in the ink, the dye becomes crystalline. A phenomenon was observed in which the transparency of the obtained pixel was reduced, and the bleeding occurred in the pixel due to the temporal migration of the dye forming the pixel due to the incomplete evaporation of the solvent. In some cases, the remaining solvent in the pixel may cause a decrease in adhesion due to some interaction with the substrate, and a decrease in light resistance due to the influence of active oxygen or the like due to thermal decomposition. Therefore, when viewed as an ink for forming a color filter, an ink that satisfies the above-described characteristics a) to d) at a higher level is preferable.

On the other hand, it is needless to say that the inkjet ink preferably has stable ejection performance and ejection accuracy.

According to the study of the present inventors, the problem and the required characteristics in the formation of the blue pixel portion of the color filter described above are achieved by using a blue dye composed of a porphyrazine derivative having a nitrogen-containing aromatic ring. I got the knowledge that I can do it.

An object of the present invention is to provide a blue dye suitable for forming a blue pixel portion of a color filter. Another object of the present invention is to provide an ink which satisfies the above characteristics a) to e) at a higher level and is suitable for forming a color filter having excellent ejection stability and landing point accuracy. Another object of the present invention is to provide a color filter provided with a blue filter portion having excellent transparency, light resistance and heat resistance.

Another object of the present invention is to provide a low-cost method for producing a color filter having a blue filter portion having high transparency, low bleeding and excellent adhesion. Another object of the present invention is to provide a high quality liquid crystal panel. Another object of the present invention is to provide a computer having a high-quality image display unit.

[0018]

The porphyrazine derivative having a nitrogen-containing aromatic ring of the present invention as a blue dye capable of achieving the above object has a structure represented by the following formula (1). And

[0019]

Embedded image [In the formula, A _{1 to} A ₄ each independently represent an aromatic ring optionally substituted with a halogen atom, a nitro group, an alkyl group, an aryl group, an alkoxy group, a sulfone group or a sulfamide group, or a sulfone group or a sulfamide. a nitrogen-containing heteroaromatic ring optionally substituted with a group, also a ₁ ~
At least one of A ₄ is a nitrogen-containing heterocyclic ring. M is two hydrogen atoms or a divalent metal, or a trivalent or tetravalent metal derivative, and D is a monovalent alkali metal or NH
Indicates ₄ . ]

The ink for inkjet recording according to one embodiment of the present invention, which can achieve the above object, includes a porphyrazine derivative having a nitrogen-containing aromatic ring as a dye in an ink containing a dye and a liquid medium. It is characterized by the following.

According to another aspect of the present invention, there is provided a color filter including a light-transmitting substrate and a blue color pixel at a predetermined position on the substrate. The colored pixels include a dye composed of the above porphyrazine derivative having a nitrogen-containing aromatic ring.

A liquid crystal panel according to one embodiment of the present invention which can achieve the above object includes a light-transmitting substrate and a blue colored pixel at a predetermined position on the substrate, and the colored pixel is A color filter containing a pigment comprising a porphyrazine derivative having a nitrogen-containing aromatic ring, and a panel substrate disposed to face the color filter, wherein a liquid crystal compound is sealed between the color filter and the panel substrate. It is characterized by being.

A computer according to one embodiment of the present invention, which can achieve the above object, includes a light-transmitting substrate,
And a color filter including a color filter including a porphyrazine derivative having a nitrogen-containing aromatic ring and a blue color pixel at a predetermined position on the substrate, and a panel substrate disposed to face the color filter. And a liquid crystal panel in which a liquid crystal compound is sealed between the color filter and the panel substrate as an image display unit.

One embodiment of a method for manufacturing a color filter which can achieve the above object is to provide an ink containing a dye comprising a porphyrazine derivative having a nitrogen-containing aromatic ring by using an ink-jet method on a light-transmitting substrate. And forming a colored pixel by ejecting the liquid toward the substrate and attaching it to a predetermined position on the substrate.

Another embodiment of a method for producing a color filter which can achieve the above object is an ink-jet method in which an ink containing a dye comprising a porphyrazine derivative having a nitrogen-containing aromatic ring and a curable resin is used. And discharging the liquid to a light transmissive substrate, attaching the liquid to a predetermined position on the surface of the substrate, and then curing the curable resin in the ink to form a colored pixel.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Each embodiment of the present invention will be described below.

(Dye) The blue dye used in the present invention is a porphyrazine derivative having a nitrogen-containing aromatic ring having the structure represented by the above formula (1).

Examples of the aromatic ring or nitrogen-containing heteroaromatic ring which can constitute A _{1 to} A ₄ in the formula (1) include those having the structures represented by the following formulas (3) to (9). However, all of A _{1 to} A ₄ do not take the structure of the formula (9) at the same time.

[0029]

Embedded image

In the above (3) to (8), R _{1 to} R ₁₄ are each independently a hydrogen atom, a sulfone group or a sulfamide group, and in the above formula (9), R _{15 to} R ₁₈ are each independently May be substituted with a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a nitro group, or a linear or branched alkyl group having 1 to 3 carbon atoms. C1-C6 alkyl group, C1-C3
An aryl group which may be substituted with a linear or branched alkyl group, a linear or branched alkoxyl group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, an n-propoxy group) , N-butoxy group), a sulfone group and a sulfonamide group.

As the divalent metal as M, Cu, Z
n, Fe, Co, Ni, Ru, Pb, Rh, Pd, P
t, Mn, Sn and Pb can be mentioned. Examples of the trivalent or tetravalent metal derivative as M include AlCl,
InCl, FeCl, MnOH, SiCl, SnC
l ₂ , GeCl ₂ , Si (OH) ₂ , Sn (OH) ₂ , Ge
(OH) ₂ , VO and TiO. Particularly, Cu, Ni, Co, FeCl, Zn, VO, Pd and MnOH are preferable.

The following compounds (a) to (k) are typical examples of the porphyrazine derivative represented by the formula (1).

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

The porphyrazine derivative of the formula (1) can be produced, for example, by reacting a nitrogen-containing aromatic dicyano compound represented by the following formula (10) with a metal derivative such as cuprous chloride.

[0038]

Embedded image [X _{1 to} X ₄ each independently represent a carbon atom or a nitrogen atom which may be substituted, and at least two of them are substituted and are carbon atoms. ]

Alternatively, it can be obtained by reacting a nitrogen-containing aromatic dicarboxylic acid derivative represented by the following formula (11) with a metal derivative such as cuprous chloride and urea.

[0040]

Embedded image [X _{1 to} X ₄ each independently represent a carbon atom or a nitrogen atom which may be substituted, and at least two of them are substituted and are carbon atoms. ]

In addition, in a method for synthesizing a phthalocyanine derivative such as phthalimide having a nitrogen-containing aromatic ring in general, an intermediate having a nitrogen-containing aromatic ring can be used to appropriately synthesize a desired porphyrazine derivative. It is.

The amounts of the metal derivative and the intermediate having a nitrogen-containing aromatic ring used in the synthesis of the porphyrazine derivative according to the present invention are preferably in the range of 1: 3 to 1: 6 by mole. Furthermore, it is also possible to mix different kinds of nitrogen-containing aromatic ring intermediates and react them with a metal derivative to synthesize a porphyrazine derivative containing several types of aromatic rings simultaneously in the same molecule. At this time, the synthesis may be performed by mixing an aromatic ring containing no nitrogen, for example, phthalic anhydride, but the synthesis is performed so that at least one aromatic ring having a nitrogen atom is included.

As an example, the following compound L which is an intermediate having a structure similar to that of phthalocyanine is obtained by reacting 2,3-pyridinecarboxylic acid and phthalic acid at a molar ratio of 1: 1.

[0044]

Embedded image Can be synthesized, and the porphyrazine derivative of the present invention can be obtained by introducing an amidated sulfonic acid group into this as needed.

The synthesis reaction is preferably performed in the presence of a suitable solvent. At this time, the solvent has a boiling point of 1
An organic solvent of 30 ° C. or higher is preferably used. For example,
Trichlorobenzene, nitrobenzene, quinoline, chloronaphthalene, n-amyl alcohol, n-hexanol, cyclohexanol, 2-methyl-1-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 2-ethylhexanol, benzyl alcohol , Ethylene glycol, propylene glycol, ethoxyethanol, propoxyethanol, butoxyethanol, dimethylaminoethanol, diethylaminoethanol, sulfolane, and the like, but are not limited thereto. The amount of the solvent used for the synthesis can be 1 to 100 times, preferably 5 to 20 times the weight of the nitrogen-containing aromatic ring dicarboxylic acid derivative or the nitrogen-containing aromatic ring dicyano compound as an intermediate.

As the central metal, the metals mentioned in the formula (1) can be used. In the synthesis, a metal derivative to be used is selected so that a desired metal or a metal derivative is located at the center.

Further, in the synthesis reaction, 1,3-diazabicyclo [5.4.0] -7-undecene (DBU)
Alternatively, ammonium molybdate may be added.
The addition amount is 0.1 mol per 1 mol of the phthalonitrile compound.
The molar ratio can be 10 to 10 times, preferably 0.5 to 2 times.

The reaction temperature is from 80 to 300 ° C., preferably from 130 to 230 ° C. If the temperature is lower than 80 ° C., the reaction may be extremely slow, and if it is higher than 300 ° C., the porphyrazine derivative may be decomposed. The reaction time is
It can be 2 to 20 hours, preferably 5 to 15 hours. If the time is less than 2 hours, many unreacted raw materials exist,
If the time is exceeded, the porphyrazine derivative may be decomposed.

The porphyrazine derivative according to the present invention comprises
It is characterized by having a sulfone group in order to obtain good solubility as a dye used in ink jet ink. Introduction of a sulfone group into the molecule, a nitrogen-containing aromatic dicarboxylic acid derivative containing a sulfone group as an intermediate,
Alternatively, a sulfone group may be introduced after using a nitrogen-containing aromatic dicyano compound or by synthesizing an intermediate having a phthalocyanine-like structure without a sulfone group as described above. As a method for introducing a sulfone group into an intermediate having a phthalocyanine-like structure, for example, a method in which the intermediate is heated in chlorosulfonic acid in an amount of 1 to 20 times by weight, preferably 5 to 10 times by weight of the intermediate is used. Can be mentioned. At this time, the reaction temperature can be 90 to 150 ° C, preferably 120 to 140 ° C, and the reaction time can be 1 to 12 hours, preferably 4 to 6 hours. Whether sulfone group is added, for example, after the addition reaction completion of sulfone group, purified porphyrazine derivative of interest, which was analyzed by FT-IR, 1290cm ^-1 and 1120cm
^It can be confirmed by observing the sharp absorption at ^-1 .

Further, a part of the sulfone group in the porphyrazine derivative according to the present invention is used to enhance the affinity with the ink receiving layer when an ink receiving layer is used as a substrate in the production of a color filter, or to prevent water resistance. It may be further amidated to improve the properties. As a method of this amidation, in the sulfonation step, a sulfochloride of a porphyrazine derivative obtained by heating an intermediate having a phthalocyanine-like structure in chlorosulfonic acid is reacted with ammonia, The porphyrazine derivative may be converted to sulfochloride using a chlorinating agent such as thionyl chloride, and then reacted with ammonia for amidation. Since the sulfochloride of the porphyrazine derivative is easily hydrolyzed, a high yield can be obtained by gradually reacting it at ice temperature.

As the blue dye used in the present invention, the above-mentioned dye composed of a porphyrazine derivative may be used in combination with a pigment composed of a phthalocyanine derivative. As the phthalocyanine derivative, for example, the following formula (2)
Can be mentioned.

[0052]

Embedded image [Wherein, m is the number of sulfone groups, n is the number of sulfonamide groups, D is an alkali metal or ammonia, M is 2 hydrogen atoms or 2
It represents a valent metal or a trivalent or tetravalent metal derivative. ]

Examples of the alkali metal as D include, for example, monovalent alkali metals. Examples of the divalent metal as M include, for example, copper, zinc, iron, cobalt, nickel, ruthenium, lead, rhodium, palladium, platinum, tin, etc., and trivalent or tetravalent metal derivatives As, for example, AlCl, InCl,
FeCl, MnOH, SiCl, SnCl ₂ , GeC
l ₂ , Si (OH) ₂ , Sn (OH) ₂ , Ge (OH) ₂ ,
VO, TiO and the like can be mentioned.

Specific examples of the pigment comprising the phthalocyanine derivative include C.I. I. Direct Blue 8
6, 87, 199 and the like.

(Ink for Inkjet Recording) The ink for inkjet recording according to one embodiment of the present invention comprises:
The porphyrazine derivative having a nitrogen-containing aromatic ring described above as a dye constituting a coloring material of the ink, and a phthalocyanine derivative as required. This ink can be suitably used, for example, as ink for forming a blue pixel of a color filter.

When these pigments are combined, the weight ratio of the porphyrazine derivative to the phthalocyanine derivative in the ink can be selected from the range of 10: 0 to 1: 9, and particularly, 3: 7 to 7: 3. if you did this,
This is preferable because a blue pixel having excellent optical characteristics can be obtained.

The total amount of the dye in the ink is 0.1 to 15% by weight (% by weight) based on the total weight of the ink.
Particularly, in the range of 1 to 10% by weight, and more preferably in the range of 2 to 8% by weight, satisfactory optical characteristics can be carried in the pixel and the characteristics of the ink deviate from the range in which the ink can be ejected accurately by the ink jet recording method. This is preferable without any change.

The above-mentioned dye is held in a dissolved state, a dispersed state or a dissolved and dispersed state, and as a medium constituting the ink, for example, an aqueous medium containing water can be used. The proportion of water as a component of the aqueous medium is 10 to 90% by weight, especially 20% by weight based on the total weight of the ink.
It is preferable to set it to 80% by weight.

Further, the aqueous medium may contain a water-soluble organic solvent. For example, by using a water-soluble organic solvent as described below, it is possible to improve the solubility of the ink constituents, adjust the viscosity, and the like. Particularly, a water-soluble organic solvent having a boiling point of about 150 to 250 ° C. The solvent ejects the ink using an ink jet recording method and, when attaching the ink to the substrate, reduces the possibility of clogging of the orifice and does not reduce the adhesion to the substrate. Therefore, it is suitably used. Further, the content of the water-soluble organic solvent is such that the boiling point is 150 to 2 with respect to the total amount of the ink.
The organic solvent at 50 ° C contains 5 to 50% by weight, more preferably 5 to 50% by weight of the organic solvent having a boiling point of 180 to 230 ° C. In addition, the organic solvent having a boiling point of 250 ° C. or more is more preferably 30% by weight or less, and the boiling point is 23% or less.
More preferably, the organic solvent at 0 ° C. or higher is 20% by weight or less. Representative examples of organic solvents that can be used are shown in Tables 1 and 2.

[0060]

[Table 1]

[0061]

[Table 2]

Further, a nonionic, anionic or cationic surfactant may be used in the ink. In addition, additives such as a pH adjuster and a fungicide may be added as necessary. May be.

By the way, such an ink is ejected from a recording head by an ink jet method, for example, a bubble jet type using an electrothermal converter as an energy generating element, or a piezo jet type using a piezoelectric element, etc. It is very suitably used to form a blue pixel when deposited on top. As a characteristic of this ink, at the time of ink preparation, the surface tension is 30 to 68 when the ink temperature is 25 ° C.
By setting the dyn / cm and the viscosity to 15 cP or less, particularly 10 cP or less, and more preferably 5 cP or less, the ink ejection characteristics become particularly excellent. And in this embodiment,
Specific ink compositions that can achieve such characteristics include, for example, the inks described in Examples described later.

The ink used in the present invention preferably further contains a curable resin. As this curable resin,
A resin that can be cured by light or heat can be used,
For example, a copolymer using an acrylic monomer can be suitably used. Acrylic monomers that can constitute this copolymer include N, N-dimethylolacrylamide, N, N-dimethoxymethylacrylamide,
Examples thereof include N-diethoxymethylacrylamide, N, N-dimethylol methacrylamide, N, N-dimethoxymethyl methacrylamide, and N, N-diethoxymethyl methacrylamide. These monomers can be used alone or in combination of two or more.

Other monomers copolymerized with the acrylic monomer include vinyl monomers, styrene, α-methylstyrene, acrylamide methacrylamide, acrylonitrile, allylamine, vinylamine, vinyl acetate, vinyl propionate and the like. Or a combination of two or more thereof. Examples of the vinyl monomer include acrylic acid,
Acrylic esters such as methacrylic acid, methyl acrylate and ethyl acrylate; containing hydroxyl groups such as methacrylic esters such as methyl methacrylate and ethyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate and hydroxyethyl acrylate A vinyl monomer can be mentioned.

Furthermore, other photocurable resins, photopolymerization initiators and the like can be added to the ink within a range that does not impair the effects of the present invention. Further, an acrylic resin, an epoxy resin, or the like may be used in combination. The amount of the curable resin in the ink can be selected according to the desired ink composition, but is preferably, for example, 0.1 to 5% by weight.

(Method for Manufacturing Color Filter Using Ink) Next, a method for manufacturing a color filter using the above-described ink will be described. FIG. 1 is an explanatory diagram of a method for manufacturing a color filter for liquid crystal according to one embodiment of the present invention.
FIG. 1A shows a light-transmitting substrate 1 (for example, a glass substrate or the like) on which a light-shielding portion (hereinafter referred to as a “black matrix”) 2 is formed in a pattern. When the black matrix 2 is formed directly on a substrate, for example, a method of forming a thin film of a metal (for example, chromium, chromium oxide, or the like) by sputtering or vapor deposition and patterning the thin film by a photolithography process may be used. When it is provided on an object, a patterning method by a general photolithography process may be used.

First, a layer (ink receiving layer) 3 containing a curable resin composition is formed on the substrate 1 on which the black matrix 2 is formed (FIG. 1B).

The substrate 1 can be made of a material that can satisfy the characteristics required for a color filter such as light transmittance (transparency) and mechanical strength. For example, a glass plate,
Acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, ethylene resin, polyolefin copolymer resin, vinyl chloride copolymer resin,
A film or plate made of a resin such as a vinylidene chloride copolymer resin can be used. Further, when a pixel portion is directly provided in various products, for example, a substrate on which a black matrix for a liquid crystal display is formed, or a substrate on which a liquid crystal display semiconductor element such as a TFT or STN is formed is used as the substrate 1.

As the material for forming the ink receiving layer 3, known materials can be used. For example, in consideration of heat resistance and the like, acrylic resins, epoxy resins, and imide resins are preferable. Considering the properties, those containing a cellulose-based water-soluble polymer such as hydroxypropylcellulose, hydroxyethylcellulose, methylcellulose and carboxymethylcellulose are preferable. Other examples include natural resins such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetal, polyurethane, carboxymethyl cellulose, polyester and the like, and albumin, gelatin, casein, starch, cationized starch, gum arabic, sodium alginate and the like. In particular, in consideration of the transparency of the colored portion, bleeding, light resistance of the dye, and the like in addition to the heat resistance and the ink absorbency, a mixture of hydroxypropylcellulose and methylolated melamine, or a compound represented by the following formula (x): It is preferable to use at least a single monomer that supplies the structural unit to be used and / or a copolymer with another vinyl monomer.

[0071]

Embedded image

In the above formula (x), R ₁₉ is H or C
H ₃ etc., R ₂₀ represents an alkyl group which may be substituted with a straight-chain or branched alkyl group H or unsubstituted or C1-5 like. Examples of the monomer for supplying the structural unit represented by the formula (x) include N-methylolacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-isopropoxymethylacrylamide, and N-methylol Methacrylamide, N-methoxymethyl methacrylamide,
N-ethoxymethyl methacrylamide and the like.
Other vinyl monomers include acrylic acid, methacrylic acid, acrylates (eg, methyl acrylate, ethyl acrylate), methacrylates (eg, methyl methacrylate, ethyl methacrylate), and vinyl containing hydroxyl groups. System monomers (hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, etc.), styrene, α-methylsterene, acrylamide, methacrylamide, acrylonitrile, allylamine, vinylamine, vinyl acetate, vinyl propionate and the like. Can be. The copolymerization ratio between the monomer corresponding to the structural unit of the above formula (x) and another vinyl monomer is 95: 5 to 5: 5 in molar ratio.
A range of 5:95 is desirable.

The receiving layer 3 may contain various additives as necessary. Specific examples of additives include various surfactants, dye fixatives (waterproofing agents), defoamers, antioxidants, fluorescent brighteners, ultraviolet absorbers, dispersants, viscosity adjusters, and pH adjusters. , A fungicide and a plasticizer. These additives may be arbitrarily selected from conventionally known compounds according to the purpose.

As a method for forming the ink receiving layer 3, methods such as spin coating, roll coating, bar coating, spray coating, and dip coating can be used. Prebaking may be performed as needed.

Next, the ink according to the present invention described above is applied to a pixel forming portion of the ink receiving layer 3 by an ink jet method, and a predetermined portion of the ink receiving layer 3 is colored (FIG. 1C). As the ink jet method, a bubble jet type using an electrothermal converter or a piezo jet type using a piezoelectric element can be used as the energy generating element, and the coloring area and the coloring pattern can be set arbitrarily. Here, a preferred method for forming pixels by ejecting ink by an ink-jet method will be described with reference to FIG. 2. FIG. 2 is a block diagram showing a configuration of an apparatus for drawing a colored portion of a color filter by an ink-jet method. is there. In FIG. 2, the CPU 21
Is connected to the inkjet recording head 4 via a head drive circuit 22. Further, the CPU 21 is configured so that control program information in the program memory 23 is input. Then, the CPU 21 moves the ink jet recording head 23 to a predetermined position on the substrate 1 (not shown), brings a desired pixel position on the substrate 1 below the ink jet head, and places a desired color ink 24 on the position.
Is discharged for coloring. By performing this for a desired pixel position on the substrate 1, a color filter can be manufactured.

When the color filter to be created has R, G, and B pixels, G and R
As the ink used for forming the pixel of the present invention, a known ink is used as appropriate, and simultaneously with the ink B of the present invention, or
A predetermined portion of the ink receiving layer 3 may be dyed for each color to form R, G, and B pixels.

Next, the ink receiving layer 3 is cured (FIG. 1).
(D)). As a curing method, a method suitable for the curable resin used for the ink receiving layer may be used. For example, heating, light irradiation, or heating and light irradiation are performed to cure to form colored pixels of each color. Here, the light to be applied to the ink absorbing layer is not particularly limited.
UV light is preferable, and light irradiation conditions are 1 to 300.
About 0 mJ / cm ² is preferable. Examples of the heat treatment include a method using an oven, a hot plate, or the like. The heat treatment may be performed at a temperature of 50 ° C. to 180 ° C. for 10 seconds to 20 minutes.

Thereafter, a protective layer is formed on the cured ink receiving layer 3 as required (FIG. 1E). The protective layer 6 can be provided by applying a resin material curable by, for example, light irradiation or heat treatment, and subsequently curing the resin material, or by forming an inorganic film by vapor deposition or sputtering. As a material that can be used for the protective layer, a material that does not impair the transparency required for the color filter when the protective layer is formed and that can withstand the ITO forming process or the alignment film forming process that is performed as necessary thereafter is preferable. Specifically, for example, an organic material includes an acrylic resin such as epoxy acrylate and urethane acrylate, and an inorganic material includes SiO ₂ . Thus, the color filter 9 according to the present embodiment can be obtained.

Next, a method of manufacturing a color filter without providing the ink receiving layer 3 will be described with reference to FIG.

First, a substrate having a black matrix 2 formed on the surface in the same manner as described above is prepared (FIG. 3).
(A)). In addition, an appropriate thickness (for example, 0.
It is preferable to make a wall of about 8 μm or more). Such a wall can be formed by, for example, patterning a black resin resist so that the black matrix 2 has a desired thickness when forming the black matrix 2.

Next, as shown in FIG. 3 (b), the blue (B) ink 53 according to the present invention and various known red (R) inks
1 and green (G) ink 52 are applied so as to fill the light transmitting portions 55 between the black matrices 2. At this time, it is preferable that each color ink is applied so as not to overlap on the black matrix 2. As the B ink used here, a porphyrazine derivative having a nitrogen-containing aromatic ring described above and, if necessary, a phthalocyanine derivative are used, and it is preferable that the ink further contains a curable resin. It is preferable to use the G ink and the R ink containing the resin.

Next, as shown in FIG.
Heating or both light irradiation and heating are performed to partially cure the ink applied to the openings 55 on the substrate 1 and then to FIG.
As shown in (d), the curable resin composition is applied so as to cover the colored portion 54 formed by the black matrix 2 and the ink of each color, and the colored portion 54 is completely cured by light irradiation and / or heat treatment. Thus, the colored pixel 17 is completed, and the curable resin composition is cured to form the protective layer 6, thereby obtaining a color filter. The protective layer 6 may be formed by curing a resin material that can be cured by light irradiation or heat treatment, or both, or may be formed by depositing or sputtering an inorganic film to form the protective film 6. Materials that can be used for forming the protective film 6 include:
It has the transparency of a color filter,
What can withstand a TO formation process, a light distribution film formation process, etc. can be used suitably.

(Liquid Crystal Panel) The color filter 9 which can be formed by the above-described method is, for example, as shown in FIG. 4, a color filter 9 and a substrate 14 are arranged opposite to each other, and a liquid crystal composition 12 is sealed therebetween. Thus, a liquid crystal panel can be formed. FIG. 4 shows a sectional view of an example of a TFT color liquid crystal panel incorporating the color filter of the present invention.
That is, the color liquid crystal panel is formed by aligning the substrate 14 facing the color filter 9 and sealing the liquid crystal composition 12 therebetween. TFTs (not shown) and transparent pixel electrodes 13 are formed in a matrix on the inside of one substrate of the liquid crystal panel. On the surface of the protective layer 5 of the color filter 9, a transparent opposing (common) electrode 10 is formed on one surface. Further, an alignment film 11 is formed on an inner surface of the counter substrate 14 so as to cover the pixel electrode 13, and an alignment film 11 is formed on an inner surface of the counter electrode 10. By subjecting these alignment films to a rubbing treatment, liquid crystal molecules can be arranged in a certain direction.
In the liquid crystal panel thus manufactured, a polarizing plate 15 is adhered to the outside of the color filter substrate 1 and the counter substrate 14, and the liquid crystal compound is generally backed using a backlight in which a fluorescent lamp and a scattering plate are combined. Display can be performed by functioning as an optical shutter that changes the transmittance of the light 16 of the light. The black matrix and the colored portion are usually formed on the color filter substrate side as shown in FIG. 6, but their positions are changed depending on the structure of the liquid crystal panel. For example, in a black matrix (BM) on-array type liquid crystal panel, the BM is formed on the opposite TFT substrate side as shown in FIG. 7, and in a color filter (CF) on-array type, the CF section is shown in FIG.
It is formed on the TFT substrate side as shown in FIG. The liquid crystal panel thus created is used as a pixel display device 92 such as a computer 91 as shown in FIG.

[0084]

Next, each embodiment of the present invention will be described more specifically with reference to examples.

Synthesis Example 1 Synthesis of Compound a Pyridine-2,3 was placed in a vessel equipped with a stirrer and a reflux condenser.
16.91 g of dicarboxylic acid, 21 g of urea, 0.62 g of ammonium molybdate, 6.75 g of anhydrous copper chloride,
100 ml of 1,2,4-trichlorobenzene is charged,
Heat at 200 ° C. for 5 hours. After completion of the reaction, the reaction product was cooled to room temperature, and the reaction product was washed with ethanol, water and 3% HCl to obtain a porphyrazine compound. The results of elemental analysis of the obtained compound were as follows.

Elemental analysis: Calculated value (%); C: 65.76, H: 4.65, N:
8.07 actual value (%); C: 65.93, H: 4.87, N:
8.11 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption property of the aqueous solution was λmax = 583.2 nm.

Synthesis Example 2 Synthesis of Compound b The same operation as in Synthesis Example 1 was carried out except that pyridine-2,3-dicarboxylic acid in Synthesis Example 1 was replaced with 16.91 g of pyridine-3,4-dicarboxylic acid. Was. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 57.98, H: 2.09, N: 2
8.98 actual value (%); C: 57.85, H: 1.98, N: 2
8.99 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption characteristics of the aqueous solution were λmax = 591.2 nm.

Synthesis Example 3 Synthesis of Compound c Synthesis Example 1 was the same as Synthesis Example 1 except that pyridine-2,3-dicarboxylic acid was replaced by 8.46 g of pyridine-2,3-dicarboxylic acid and 7.41 g of phthalic anhydride. The same operation as in Example 1 was performed. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 62.33, H: 2.44, N: 2
4.23 actual value (%); C: 62.18, H: 2.34, N: 2
4.23 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption property of the aqueous solution was λmax = 593.5 nm.

Synthesis Example 4 Synthesis of Compound d Synthesis Example 1 was repeated except that pyridine-2,3-dicarboxylic acid in Example 1 was replaced with 8.46 g of pyridine-3,4-dicarboxylic acid and 7.41 g of phthalic anhydride. The same operation as in Example 1 was performed. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%): C: 62.33, H: 2.44, N: 2
4.23 actual value (%); C: 62.18, H: 2.34, N: 2
4.32 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption property of the aqueous solution was λmax = 599.4 nm.

Synthesis Example 5 Synthesis of Compound e The same operation as in Synthesis Example 1 was performed except that pyridine-2,3-dicarboxylic acid in Synthesis Example 1 was changed to 16.81 g of pyrazine-2,3-dicarboxylic acid. Was. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 49.36, H: 1.38, N: 3
8.38 Found (%); C: 49.42, H: 1.28, N: 3
8.29 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption property of the aqueous solution was λmax = 582.7 nm.

Synthesis Example 6 Synthesis of Compound f The same operation as in Synthesis Example 1 was performed except that pyridine-2,3-dicarboxylic acid in Synthesis Example 1 was changed to 16.81 g of pyrimidinedicarboxylic acid. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 49.36, H: 1.38, N: 3
8.38 Found (%); C: 49.33, H: 1.19, N: 3
8.25 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption characteristic of the aqueous solution was λmax = 580.1 nm.

Synthesis Example 7 Synthesis of Compound g The same operation as in Synthesis Example 1 was carried out except that pyridine-2,3-dicarboxylic acid in Synthesis Example 1 was replaced with 16.81 pyridazine-2,3-dicarboxylic acid. Was. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 49.36, H: 1.38, N: 3
8.38 Found (%); C: 49.31, H: 1.32, N: 3
8.32 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption property of the aqueous solution was λmax = 581.9 nm.

Synthesis Example 8 Synthesis of Compound h The same operation as in Synthesis Example 1 was performed, except that pyridine-2,3-dicarboxylic acid in Synthesis Example 1 was replaced with 16.81 g of pyridazine-3,4-dicarboxylic acid. Was. The results of elemental analysis of the obtained porphyrazine compound were as follows.

Calculated value (%); C: 49.36, H: 1.38, N: 3
8.38 Found (%); C: 49.42, H: 1.33, N: 3
8.24 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption characteristic of the aqueous solution was λmax = 582.1 nm.

Synthesis Example 9 Synthesis of Compound i Pyridine-2,3 was placed in a vessel equipped with a stirrer and a reflux condenser.
8.46 g of dicarboxylic acid, 4-sulfophthalic acid
41 g, urea 21 g, ammonium molybdate 0.6
2 g, 6.758 g of anhydrous copper chloride, and 100 ml of 1,2,4-trichlorobenzene were charged and heated at 200 ° C. for 5 hours. After completion of the reaction, the reaction product was cooled to room temperature, and the reaction product was washed with ethanol, water and 3% HCl to obtain a porphyrazine compound. The results of elemental analysis of the obtained compound were as follows.

Elemental analysis: Calculated value (%); C: 46.07, H: 1.55, N: 1
7.91 found (%); C: 46.12, H: 1.32, N: 1
7.85 The absorption characteristics of the aqueous solution of this compound are as follows: λmax = 592.
It was 9 nm.

Synthesis Example 10 Synthesis of Compound j Pyridine-2,3 was placed in a vessel equipped with a stirrer and a reflux condenser.
-Dicarboxylic acid 8.46 g, 4-t-butylphthalic acid 1
0.21 g, 21 g of urea, 0.62 g of ammonium molybdate, 6.758 g of anhydrous copper chloride, and 100 ml of 1,2,4-trichlorobenzene were added and heated at 200 ° C. for 5 hours. After completion of the reaction, the reaction product was cooled to room temperature, and the reaction product was washed with ethanol, water and 3% HCl to obtain a porphyrazine compound. The results of elemental analysis of the obtained compound were as follows.

Elemental analysis: Calculated value (%); C: 66.12, H: 4.38, N: 2
0.29 actual value (%); C: 66.23, H: 4.44, N: 2
0.25 5 g of the compound obtained here was added to 50 g of chlorosulfonic acid and heated at 125 ° C. for 6 hours. After allowing to cool, the reaction solution was dropped into ice water and neutralized with NaOH. After the obtained compound was desalted and purified, it was measured by FT-IR. As a result, sharp absorption was observed at 1344 cm ^-1 and 1152 cm ^-1 , confirming that sulfonation was performed. The light absorption characteristics of the aqueous solution were λmax = 594.2 nm.

Synthesis Example 11 Synthesis of Compound k Pyridine-2,3 was placed in a vessel equipped with a stirrer and a reflux condenser.
8.46 g of dicarboxylic acid, 4-sulfophthalic acid
41 g, urea 21 g, ammonium molybdate 0.6
2 g, 9.17 g of anhydrous zinc acetate, and 100 ml of 1,2,4-trichlorobenzene were added and heated at 200 ° C. for 5 hours. After completion of the reaction, the reaction product was cooled to room temperature, and the reaction product was washed with ethanol, water and 3% HCl to obtain a porphyrazine compound. The results of elemental analysis of the obtained compound were as follows.

Elemental analysis: Calculated value (%); C: 45.96, H: 1.54, N: 1
7.87 Found (%); C: 46.01, H: 1.62, N: 1
7.73 The absorption characteristics of an aqueous solution of this compound were as follows: λmax = 601.
It was 5 nm.

Example 1 4.0% by weight of a dye, 39.0% by weight of ethylene glycol monobutyl ether (boiling point: 170 ° C.), 6.0% by weight of ethyl alcohol (boiling point: 78 ° C.), and 51.0% by weight of water were prepared in the usual manner. To prepare R, G and B inks, respectively. The following pigments were used. R ink: C.I. I. Acid Red 158 G ink: C.I. I. Acid Green 25B ink: Combination of two dyes shown in Table 4 A-1 to 12 On a glass substrate provided with a black matrix made of chromium having openings having a size of 60 to 150 μm, N was used as an ink receiving layer. -A curable resin composition composed of a copolymer of methylol acrylamide and hydroxyethyl methacrylate (1: 1, molar ratio) is spin-coated so as to have a thickness of 1.2 µm, and prebaked at 120 ° C for 20 minutes. Was. Next, R, G, and B inks previously prepared using an inkjet printer were applied to predetermined portions to color the R, G, and B matrix patterns. Next, baking is performed at 230 ° C. for 50 minutes to accelerate the curing reaction, and after drying, a two-component acrylic thermosetting resin material (trade name: SS-7625,
(Nippon Synthetic Rubber Co., Ltd.) was spin-coated so as to have a thickness of 1 μm after curing, and heat-treated at 240 ° C. for 20 minutes to be cured to form a protective layer. A color filter having a similar structure was obtained. The obtained color filters were evaluated for the following items. Table 5 shows the results.

Evaluation 1: Transparency of colored part A liquid crystal panel was prepared using a color filter, and B (blue)
The transparency of the pattern portion was evaluated by visually dividing the pattern portion into three groups on a three-wavelength tube backlight. A: good transparency B: somewhat poor transparency C: more dull than those of A and B

Evaluation 2: Heat resistance The color filter was allowed to stand in an oven at 250 ° C. for 1 hour, and the magnitude of the discoloration and fading of the B pattern was determined by CIE.
E was calculated and evaluated according to the following criteria. A: ΔE is 10 or less B: ΔE is more than 10 and 20 or less C: ΔE is more than 20

Evaluation 3: Light fastness A color filter was irradiated with xenon light for 50 hours using an Atlas Fademeter Ci35, and the magnitude of the discoloration and fading of the B pattern portion was calculated as ΔE determined by CIE. Evaluation was based on criteria. A: ΔE is 10 or less B: ΔE is more than 10 and 20 or less C: ΔE is more than 20

Evaluation 4: Landing position accuracy Nozzle density 360d
An ink jet printer equipped with a recording head having pi (nozzle pitch of 70.4 μm) and 64 nozzles is filled with G ink, and all nozzles are simultaneously driven to draw one straight line of 64 dots every 0.5 seconds. Repeat 200 times,
The landing position accuracy was evaluated based on the following criteria. A: The number of dots that deviate from the straight line by at least one dot is 0.1.
%: B: The number of dots that deviate from the straight line by one dot or more is 0.1
% To less than 0.5% C: The number of dots deviating from the straight line by one dot or more is 0.5
%that's all

A series of operations such as ITO (electrode formation), alignment film formation, and liquid crystal material encapsulation were performed on the color filter manufactured as described above by a conventional method, and a color liquid crystal device having the structure shown in FIG. As a result, an element having good characteristics was obtained.

Comparative Example 1 Example 1 was repeated except that the dyes B-1 to B-3 shown in Table 4 were used.
A color filter was prepared and evaluated in the same manner as described above. Table 5 shows the evaluation results.

Example 2 R, G and B inks were prepared using the following compositions.

[0115]

[Table 3]

The following dyes were used. For R ink: C.I. I. Acid Red 118 G ink: C.I. I. For Acid Green 25B ink: Combination of two dyes A-1 to 1 shown in Table 4
2

On a glass substrate, a black pigment resist CK-S171B manufactured by Fuji Hunt Co., Ltd. was applied by spin coating, and then exposed, developed and heat-treated to a thickness of 1.0 μm.
m, a black matrix having openings with a size of 60 to 150 μm was formed. Next, using each of the above inks, the ink was filled by an ink jet printer so that predetermined R, G, and B matrices were formed in the openings of the black matrix. When the filling of the ink was completed, the ink was cured by a heat treatment at 230 ° C. for 30 minutes to obtain a color filter for a liquid crystal element having a structure similar to that shown in FIG. When this color filter was observed with an optical microscope, no problems such as color mixing and color unevenness were observed. Table 6 shows the results of the evaluation performed in the same manner as in Example 1.

Further, a series of operations such as ITO (electrode formation), alignment film formation, and liquid crystal material encapsulation were performed on the color filter thus manufactured by a conventional method, and the color liquid crystal device having the structure shown in FIG. As a result, an element having good characteristics was obtained.

Comparative Example 2 A color filter was prepared and evaluated in the same manner as in Example 2 except that the dyes shown in Table 4 were used. Table 6 shows the evaluation results.

[0120]

[Table 4]

[0121]

[Table 5]

[0122]

[Table 6]

[0123]

As described above, according to the present invention, it is possible to provide a high quality color filter, particularly a color filter having excellent characteristics in a blue pixel portion. Further, according to the present invention, it is possible to provide a dye suitable for forming the blue pixel portion of the color filter and an ink jet ink using the dye. Further, according to the present invention, it is possible to obtain an ink that satisfies the ink ejection characteristics when the ink jet recording method is used for forming the color filter. Further, according to the present invention, a liquid crystal panel having excellent characteristics and a computer using the same can be obtained.

[Brief description of the drawings]

FIG. 1 is a process chart of an example of a method for manufacturing a color filter using an inkjet method according to the present invention.

FIG. 2 is a schematic explanatory view of a method of forming a pixel of a color filter using an inkjet method.

FIG. 3 is a process chart of an example of a method for manufacturing a color filter using the inkjet method of the present invention.

FIG. 4 is a schematic sectional view of a liquid crystal panel.

FIG. 5 is an explanatory diagram of a transient phenomenon when pixels of a color filter are formed using an inkjet method.

FIG. 6 is a schematic sectional view of a liquid crystal panel.

FIG. 7 is a schematic sectional view of a liquid crystal panel.

FIG. 8 is a schematic sectional view of a liquid crystal panel.

FIG. 9 is a schematic perspective view of a computer.

[Explanation of symbols]

 Reference Signs List 1 light-transmitting substrate 2 black matrix 3 ink-receiving layer 4 inkjet recording head 5, 6 protective layer 7, 55 light-transmitting portion 9 color filter 10 common electrode 11 alignment film 12 liquid crystal compound 13 pixel electrode 14 glass substrate 15 polarizing plate 16 back Write light 17 Colored pixel section 21 CPU 22 Head drive circuit 23 Program memory 24 Ink 51 Red (R) ink 52 Green (G) ink 53 Blue (B) ink 54 Colored portion 61 Counter substrate 62 Liquid crystal composition 63 Pixel electrode 64 Common Electrodes 65, 66 Alignment film 67 Deflector 68 Backlight 69 Uncolored section 91 Computer 92 Image display section

Continuation of the front page (72) Inventor Koichiro Nakazawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshihisa Yamashita 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Mayumi Yokoyama Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo

Claims (30)

[Claims] 1. The following formula (1): [In the formula, A _{1 to} A ₄ each independently represent an aromatic ring optionally substituted with a halogen atom, a nitro group, an alkyl group, an aryl group, an alkoxy group, a sulfone group or a sulfamide group, or a sulfone group or a sulfamide. a nitrogen-containing heteroaromatic ring optionally substituted with a group, also a ₁ ~
At least one of A ₄ is a nitrogen-containing heterocyclic ring. M is two hydrogen atoms or a divalent metal, or a trivalent or tetravalent metal derivative, and D is a monovalent alkali metal or NH
Indicates ₄ . ] The porphyrazine derivative which has a nitrogen-containing aromatic ring characterized by the above-mentioned. 2. An ink-jet ink containing a dye and a liquid medium, wherein the dye contains the porphyrazine derivative according to claim 1. 3. The ink according to claim 2, further comprising a phthalocyanine derivative as a coloring matter. 4. The ink according to claim 3, wherein the phthalocyanine derivative is represented by the following formula (2). Embedded image [Wherein, m and n are the numbers of the substituents, D is each independently an alkali metal or ammonia, and M is 2
Represents a divalent metal having two hydrogen atoms or substituents, or a trivalent or tetravalent metal derivative. ] 5. A porphyrazine derivative and a phthalocyanine derivative in a weight ratio of 10: 0 to 1: 9.
Or the ink according to 4. 6. The ink according to claim 5, comprising a porphyrazine derivative and a phthalocyanine derivative in a weight ratio of 3: 7 to 7: 3. 7. The ink according to claim 3, wherein the dye concentration is 0.1 to 15% by weight based on the total weight of the ink. 8. A solvent having a boiling point of 150 to 250 ° C.
The ink according to any one of claims 3 to 7, wherein the ink content is about 10% by weight. 9. The ink according to claim 3, further comprising a curable resin. 10. The ink according to claim 9, wherein the curable resin is a resin that is cured by applying at least one of light and heat. 11. A light-transmitting substrate, and a color filter comprising a blue colored pixel at a predetermined position on the substrate, wherein the colored pixel contains the dye comprising the porphyrazine derivative according to claim 1. A color filter, characterized in that: 12. The color filter according to claim 11, wherein the substrate has a resin layer on a surface, and a part of the resin layer constitutes the colored pixel. 13. The color filter according to claim 11, further comprising a plurality of the colored pixels, wherein each of the colored pixels is separated from each other, and a light shielding layer is provided between each of the colored pixels. 14. The color filter according to claim 13, wherein a surface of said light shielding layer is non-colored. 15. The colored surface elements are spaced apart from each other, and have a light-shielding layer and a resin layer covering the light-shielding layer between the colored pixels. The color filter according to claim 11, wherein the surface is non-colored. 16. The color filter according to claim 11, wherein the blue colored pixel further contains a dye comprising a phthalocyanine derivative. 17. The color filter according to claim 16, wherein the phthalocyanine derivative has a structure represented by the following formula (2). Embedded image [Wherein, m and n are the numbers of the substituents, D is each independently an alkali metal or ammonia, and M is 2
Represents a divalent metal having two hydrogen atoms or substituents, or a trivalent or tetravalent metal derivative. ] 18. The color filter according to claim 16, wherein the porphyrazine derivative and the phthalocyanine derivative are contained in a weight ratio of 10: 0 to 1: 9. 19. The method according to claim 1, wherein the porphyrazine derivative and the phthalocyanine derivative are contained in a weight ratio of 3: 7 to 7: 3.
8. The color filter according to 8. 20. A color filter according to claim 11, and a panel substrate facing the color filter, wherein a liquid crystal compound is sealed between the color filter and the panel substrate. A liquid crystal panel characterized by the following. 21. The liquid crystal panel according to claim 20, wherein an electrode for controlling the alignment of the liquid crystal compound is provided on a surface of the light transmitting substrate of the color filter opposite to the side having the colored pixels. 22. A computer comprising the liquid crystal panel according to claim 20 as an image display unit. 23. A colored pixel is formed by ejecting the ink according to claim 2 toward a light-transmitting substrate using an inkjet method and attaching the ink to a predetermined position on the substrate. A method for manufacturing a color filter, comprising the steps of: 24. The method for producing a color filter according to claim 23, wherein the light-transmitting substrate has a resin layer on a surface. 25. The method according to claim 24, wherein the material forming the resin layer is a polymer containing at least a water-soluble acrylic monomer unit. 26. The method according to claim 24, wherein the material forming the resin layer contains at least a cellulose-based water-soluble polymer. 27. The ink according to claim 9 or 10, which is ejected toward a light-transmitting substrate surface using an ink-jet method, adheres to a predetermined position on the substrate surface, and then cures in the ink. A process for curing a color filter to form a colored pixel. 28. The method for manufacturing a color filter according to claim 27, wherein a substrate having a light-shielding layer that separates a plurality of pixels formed on the surface from each other is used as the light-transmitting substrate. 29. The method for manufacturing a color filter according to claim 32, further comprising a step of forming a curable resin layer so as to cover the colored pixels, and curing the curable resin layer. 30. The method for manufacturing a color filter according to claim 29, wherein the curable resin layer is cured by applying at least one of light energy and heat energy.