WO2018182135A1 - Blue photosensitive resin composition, color filter produced by using same, and image display device - Google Patents

Abstract

The present invention relates to a blue photosensitive resin composition, a color filter produced by using same, and an image display device, the blue photosensitive resin composition comprising scattering particles, a blue coloring, a cardo-based binder resin as a binder resin, a photoinitiator, a photopolymerizable compound and a solvent, wherein the photopolymerizable compound comprises a photopolymerizable compound comprising an alkylene oxide.

Description

Blue photosensitive resin composition, color filter and image display device manufactured using the same

The present invention relates to a blue photosensitive resin composition, a color filter manufactured using the same, and an image display device.

The color filter is a thin film type optical component that extracts three colors of red, green, and blue from white light and makes them possible in fine pixel units. The size of one pixel is about tens to hundreds of micrometers. Such a color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield the boundary between each pixel, and a plurality of colors (typically red (R), green (G) and The pixel units in which the three primary colors of blue (B) are arranged in a predetermined order are stacked in this order.

Recently, as one of the methods of implementing a color filter, a pigment dispersion method using a pigment-dispersible photosensitive resin has been applied, but a part of the light is absorbed by the color filter while the light emitted from the light source passes through the color filter. The problem is that the efficiency is lowered and the color reproduction is lowered due to the characteristics of the pigment contained in the color filter.

In order to solve this problem, a color filter manufacturing method using a self-luminous photosensitive resin composition including a quantum dot has been proposed.

Specifically, Korean Patent Publication No. 2007-0094679 suggests that color reproducibility can be improved by having a color filter layer formed of quantum dots, and Korean Patent Publication No. 2009-0036373 uses a conventional color filter as a quantum dot phosphor. It is proposed that the display quality can be improved by improving the luminous efficiency by replacing the light emitting layer.

However, until now, the photosensitive resin composition developed to manufacture a color filter has not sufficiently satisfied the requirements such as development speed control, fine pattern formation, excellent optical efficiency and viewing angle to be sufficiently used in the process.

The present invention is to control the development speed, to solve the problem caused by the process residue by eliminating the residue of the fine pattern, to improve the poor display, to implement a color filter, especially a self-luminous color filter to ensure excellent light efficiency and viewing angle It is an object of the present invention to provide a blue photosensitive resin composition capable of this, a color filter and an image display device manufactured using the same.

The present invention provides a blue photosensitive resin composition comprising a scattering particle, a blue colorant, a binder resin, a cardo-based binder resin, a photoinitiator, a photopolymerizable compound, a thermosetting agent and a solvent, wherein the photopolymerizable compound comprises an alkylene oxide. It provides a blue photosensitive resin composition characterized by including a compound.

The present invention also provides a color filter comprising a blue pattern layer made of the above-described blue photosensitive resin composition.

In another aspect, the present invention is the color filter; And a light source emitting blue light.

The present invention includes a photopolymerizable compound containing alkylene oxide in the blue photosensitive resin composition, to control the development speed, solve the problem caused by the process residue by eliminating the residue of the pattern, and poor display problems are improved In addition, the present invention provides a color filter in which the problem of resist non-developing is improved. In addition, it is possible to provide a high-quality self-luminous color filter having an excellent viewing angle by adjusting the taper.

The blue photosensitive resin composition of the present invention may include a cardo-based binder resin, a photoinitiator, a photopolymerizable compound and a solvent as scattering particles, a blue colorant, and a binder resin, and in particular, the photopolymerizable compound may include ethylene oxide or propylene oxide. By including the photopolymerizable compound, the color filter including the blue pattern layer prepared by using the blue photosensitive resin composition of the present invention can solve the problem caused by the residue on the process by controlling the development speed and eliminating the residue of the pattern. . In addition, it is possible to provide a color filter, in particular, a self-luminous color filter, in which a problem of poor display is improved and an issue of resist non-developing is improved. In addition, it is possible to provide a color filter having an excellent viewing angle, in particular a self-luminous color filter, and an image display device including the same.

Hereinafter, the configuration of the present invention will be described in detail.

Scattering particles

The scattering particles of the present invention may be a metal oxide having an average particle diameter of 10 to 1000 nm, more preferably when the average particle diameter is in the range of 30 to 500 nm. In this case, when the average particle diameter is less than the above range, sufficient scattering effect of the incident light cannot be expected, and when the average particle diameter is above the above range, the surface of the self-luminous layer of uniform quality cannot be obtained.

The metal oxide is Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Mo, Cs, Ba, La, Hf, W, Tl, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Ti, Sb, Sn, Zr, Nb, It may be an oxide including one metal selected from the group consisting of Ce, Ta, In, and combinations thereof. More specifically, Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO, Nb ₂ O ₃ , SnO, MgO and the like selected from the group It may be one or more. If necessary, a material surface-treated with a compound having an unsaturated bond such as acrylate may be used.

The scattering particles may be appropriately adjusted as necessary to the average particle diameter and the content in the entire composition to sufficiently improve the light emission intensity of the color filter.

In addition, the scattering particles may be included in 0.1 to 50% by weight relative to the total weight of solids in the blue photosensitive resin, preferably 5 to 35% by weight. When the scattering particles are in the above preferred range, the effect of increasing the light emission intensity can be obtained, and the stability of the composition can be ensured.

Blue colorant

In the blue colorant of the present invention, examples of the blue pigment include compounds classified as pigments in the color index (Published by The society of Dyers and Colourists), and more specifically, the color index (CI) as follows. Although pigment of number is mentioned, It is not necessarily limited to these. Blue pigments are specifically described, for example, in C.I. Pigment blue 15: 3, 15: 4, 15: 6, 16, 21, 28, and 76, and the like. Pigment Blue 15: 3, Pigment Blue 15: 6, Pigment Blue 16 It is preferable to include at least 1 type selected from the group which consists of.

The blue colorant of the present invention may further comprise a blue dye, which is a known dye which is described in a compound or dyeing note (color dyed yarn) classified as a dye in the color index (published by The Society of Dyers and Colourists). And dyes.

Specific examples of the dye which can be used further include

C.I. As solvent dyes,

C.I. Solvent blue 5, 35, 36, 37, 44, 45, 59, 67 and 70, and the like. More preferably at least one of Solvent Blue 35, 36, 44, 45 and 70.

In addition, C.I. As an acid dye,

CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 , 335 and 340, among others CI More preferably, it contains one or more of acid blue 80 and 90.

In addition, C.I. As a direct dye,

CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293.

CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84, etc. are mentioned.

The said blue dye can be used individually or in combination of 2 or more types, respectively.

The blue colorant of the present invention may further include a purple colorant as an additional colorant. The purple coloring agent may comprise at least one of a purple pigment and a purple dye, wherein the purple pigment is specifically C.I. Pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37 and 38, among which C.I. It is more preferred to include pigment violet 23.

Purple dyes are specifically, C.I. Solvent violet, C.I. acid violet, C.I. acid violet, C.I. modanto violet, and the like, but are not limited thereto.

Specifically, the C.I. Solvent violet is C.I. Solvent violet 8, 9, 13, 14, 36, 37, 47 and 49, and the like. More preferably, solvent violet 13 is included. C.I. acid violet includes C.I. Acid violet 6B, 7, 9, 17, 19 and 66, and the like. More preferably, acid violet 66 is included. CI direct violet includes CI direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104. .

Furthermore, CI modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58, etc. are mentioned. .

The blue colorant may be used in an amount of 0.1 to 50% by weight, preferably 0.5 to 30% by weight, based on the total weight of solids in the blue photosensitive resin. When the content of the blue colorant satisfies the above range, it is possible to suppress the reflection of external light, to effectively exhibit the emission intensity of the color, and to ensure the stability of the viscosity.

In the present invention, the blue colorant and the scattering particles are included even though the blue quantum dots are not included, thereby reducing the efficiency of the blue pixel of the color filter, particularly the self-luminous color filter.

Binder resin

The binder resin of this invention contains cardo system binder resin. The cardo-based binder resin has reactivity and alkali solubility due to the action of light or heat and acts as a dispersion medium of the coloring material. The cardo-based binder resin contained in the blue photosensitive resin composition of the present invention is not limited as long as it is a resin that acts as a binder resin for scattering particles and is soluble in an alkaline developer used in the developing step for producing a color filter.

The cardo-based binder resin of the present invention may include one or more of the compounds represented by Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

In Chemical Formula 1-1 or Chemical Formula 1-2,

이며; R ₁ , R ₂ , R ₃ and R ₄ are each independently,

Is;

X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group;

R ₅ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

In the present invention, the compound represented by Chemical Formula 1-1 may be synthesized by the compound represented by Chemical Formula 2-1, and the compound represented by Chemical Formula 1-2 may be synthesized using the compound represented by Chemical Formula 2-2. .

In the present invention, the compound represented by Chemical Formula 1-1 may be synthesized by the compound represented by Chemical Formula 2-1, and the compound represented by Chemical Formula 1-2 may be synthesized using the compound represented by Chemical Formula 2-2. .

[Formula 2-1]

[Formula 2-2]

Specifically, the compound represented by Formula 1-1 is at least one of the compounds represented by Formula 1-1-1 and Formula 1-1-2, and the compound represented by Formula 1-2 is represented by Formula 1-2- 1 and one or more compounds represented by Formula 1-2-2.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-2-1]

[Formula 1-2-2]

The cardo-based binder resin is 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3- cinnamoyl, 4-hydride Hydroxyphenyl) fluorene (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycidyl methacrylate ether) fluorene), 9,9-bis (3,4-dihydroxyphenyl) fluorene dinamic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglycidyl meta Acrylate ether spiro (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-allyl, 4-hydroxyphenylflu Orene) (9,9-bis (3-allyl, 4-hydroxyphenlylfluorene), 9,9-bis (4-allyloxyphenyl) fluorene (`9,9-bis (4-allyloxyphenyl) fluorene) and 9,9 Acid anhydrides with at least one member selected from the group consisting of bis (3,4-methacrylic diester) fluorene (9,9-bis (3,4-methacrylic diester) fluorine) Maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylene anhydrous methylenetetrahydrophthalic anhydride, anhydrous chlororenic acid, methyltetrahydrophthalic anhydride, or an acid dianhydride. It can be prepared by reacting with at least one selected from the group consisting of aromatic polyhydric carboxylic acid anhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, biphenyltetracarboxylic acid dianhydride, and bitenyl ether tetracarboxylic acid dianhydride. It is not limited.

The present invention may further include an acrylic alkali-soluble resin as a binder resin. Examples of the acrylic alkali-soluble resin include a carboxyl group-containing monomer and a copolymer with another monomer copolymerizable with the monomer. As a carboxyl group-containing monomer, unsaturated carboxylic acids, such as unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, such as unsaturated polyhydric carboxylic acid which has one or more carboxyl groups in molecules, such as unsaturated dicarboxylic acid and unsaturated tricarboxylic acid, are mentioned, for example. have. Here, as unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be mono (2-methacrylyloxyalkyl) ester thereof, for example, succinic mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl) And phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) and the like. The unsaturated polyhydric carboxylic acid may be mono (meth) acrylate of the sock end dicarboxy polymer, and examples thereof include? -Carboxypolycaprolactone monoacrylate and? -Carboxypolycaprolactone monomethacrylate. . These carboxyl group-containing monomers can be used individually or in mixture of 2 or more types, respectively. As another monomer copolymerizable with the said carboxyl group-containing monomer, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene, m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxy propyl acrylate, 3-hydroxypropyl methacrylate, 2- Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Allyl Acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nyl acrylate, dicyclopentadiethyl methacrylate, adamantyl (meth) Acrylate, norbornyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Unsaturated carboxylic acid esters; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzylmaleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And monoacryloyl or monomethacryloyl groups at the terminal of the polymer molecular chain of polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, polysiloxane. And macromonomers to have. These monomers can be used individually or in mixture of 2 or more types, respectively. In particular, bulky monomers such as monomers having a norbornyl skeleton, monomers having an adamantane skeleton, and monomers having a rosin skeleton as the other monomers copolymerizable with the carboxyl group-containing monomer are preferable because they tend to lower the dielectric constant. .

As the cardo binder resin and / or the acrylic alkali-soluble resin of the present invention, the acid value is preferably in the range of 20 to 200 (KOH mg / g). If the acid value is in the above range, the solubility in the developing solution is improved, so that the non-exposed part is easily dissolved and the sensitivity is increased, and as a result, the pattern of the exposed part remains at the time of development to improve the film remaining ratio. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration using an aqueous potassium hydroxide solution. Also, the polystyrene reduced weight average molecular weight (hereinafter, simply referred to as 'weight average molecular weight') measured by gel permeation chromatography (GPC; tetrahydrofuran as an eluting solvent) is 2,000 to 200,000, preferably 3,000 to 100,000. Cardo binder resin or acrylic alkali-soluble resin is preferable. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the non-exposed portion in the developer is excellent and the resolution tends to be improved, which is preferable.

 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the cardo-based binder resin and / or the acrylic alkali-soluble resin is preferably 1.0 to 6.0, and more preferably 1.5 to 6.0. If molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 1.5-6.0, since developability is excellent, it is preferable.

 The binder resin of the present invention may use 5 to 85% by weight, preferably 5 to 60% by weight based on the total weight of solids in the blue photosensitive resin. When the content of the binder resin is within the above range, the solubility in the developing solution is sufficient, and development residues are less likely to occur on the substrate of the non-pixel portion. It is preferable because this tends to be good.

Photopolymerizable compound

The photopolymerizable compound included in the blue photosensitive resin composition of the present invention is a compound that can be polymerized by the action of light and a photopolymerization initiator described below, and specifically, a photopolymerizable compound containing alkylene oxide, preferably ethylene oxide and / or propylene oxide. And a photopolymerizable compound containing a. When the photopolymerizable compound added with ethylene oxide and / or propylene oxide is included, various problems that may occur due to process residues can be solved by controlling the development speed, eliminating the residues of the pattern, and improving display defects. It is possible to eliminate the resist non-development, and to adjust the taper, to form an excellent viewing angle, it is possible to manufacture a device of high quality image quality.

As a photopolymerizable compound containing the said alkylene oxide, the alkylene oxide modified pentaerythritol (meth) acrylate compound, the alkylene oxide modified dipentaerythritol (meth) acrylate compound, and the alkylene oxide modified trimetholpropane ( Meta) acrylate compounds, and alkylene oxide modified glycerin (meth) acrylate compounds, and more specifically, ethylene oxide modified trimetholpropane triacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, and ethylene oxide. Modified pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hex Oh, and the like Cri rate, propoxy federated pentaerythritol polyacrylate, propoxy federated dipentaerythritol hexa acridine rate, ethoxy federated glycerol triacrylate. It is more preferable to include ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, and propoxylated pentaerythritol polyacrylate.

The blue photosensitive resin composition of this invention may further contain the conventional photopolymerizable compound which does not contain an alkylene oxide. Specifically, the photopolymerizable compound using the monofunctional monomer, bifunctional monomer, and other polyfunctional monomer which do not contain ethylene oxide and a propylene oxide is mentioned.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N-vinylpyrroli Money, etc. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate etc. are mentioned. Of these, bifunctional or higher polyfunctional monomers are preferably used. The photopolymerizable compound may be used in an amount of 5 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of solids in the blue photosensitive resin. If the photopolymerizable compound is within the above range, there is no reduction in photosensitivity, sufficient strength of the film, no loss of pattern during development, good pattern construction even in the fine pattern portion, and tendency of smoothness of the resist. desirable.

Photoinitiator

The photoinitiator used in the present invention initiates a radical reaction of the photosensitive resin composition, causes curing, improves sensitivity, and preferably contains an acetophenone-based compound. As an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2 -Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl [4- (1-methylvinyl) phenyl] propane-1- Oligomers, etc. may be mentioned, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and the like are preferable. Moreover, photoinitiators other than the said acetophenone series can be used in combination. Photopolymerization initiators other than the acetophenone series include active radical generators, sensitizers, and acid generators that generate active radicals by irradiation with light. As an active radical generating agent, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, a triazine type compound, etc. are mentioned, for example. As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoisobutyl ether, etc. are mentioned, for example. As a benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned. As a triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4dimethoxyphenyl) ethenyl] -1,3,5 -Triazine and the like. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2, -bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene Compounds and the like can be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate and 4-acetoxyphenyldimethylsulfonium p-toluenesulfo. Acetate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, benzoin tosylate, etc. are mentioned. In addition, there are some compounds which generate an acid simultaneously with the active radicals in the compound as an active radical generator, for example, a triazine photopolymerization initiator is also used as an acid generator.

The photoinitiator may be included 0.1 to 30% by weight, preferably 0.3 to 20% by weight relative to the total weight of solids in the blue photosensitive resin. If it exists in the said range, since the blue photosensitive resin composition becomes highly sensitive and the intensity | strength of the pixel part formed using this composition and the smoothness in the surface of this pixel part tend to become favorable, it is preferable.

Furthermore, in this invention, photoinitiator start adjuvant can be used. A photoinitiator adjuvant may be used in combination with a photoinitiator, and is a compound used in order to accelerate superposition | polymerization of the photopolymerizable compound in which superposition | polymerization was started by a photoinitiator. As photopolymerization start adjuvant, an amine compound, an alkoxy anthracene type compound, a thioxanthone type compound, etc. are mentioned.

 Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoic acid. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzphenone (commonly known as Michler's ketone), 4,4'-bis (diethyl Amino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable. As an alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example. Etc. can be mentioned. As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy city oxanthone etc. are mentioned. These photoinitiators (D) may be used alone or in combination of a plurality thereof. In addition, a commercially available thing can be used as a photoinitiator starter, As a commercially available photoinitiator starter, brand name "EAB-F" (manufacturer: Hodogaya Chemical Co., Ltd.) etc. are mentioned, for example.

 In the case of using these photopolymerization initiation assistants, the amount thereof is usually 10 mol or less, preferably 0.01 to 5 mol, per mol of the photopolymerization initiator. When it exists in the said range, since the sensitivity of a blue photosensitive resin composition becomes higher and the productivity of the color filter formed using this composition tends to improve, it is preferable.

solvent

The solvent contained in the blue photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of a blue photosensitive resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol Alkylene glycol alkyl ether acetates such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, methyl Ketones such as methyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, alcohols such as ethylene glycol, glycerin, ethyl 3-ethoxypropionate, Ester, such as 3-methoxy methyl propionate, Cyclic ester, such as -butyrolactone, etc. are mentioned. Among the above solvents, organic solvents having a boiling point of 100 to 200 are preferable in the solvents in terms of applicability and dryness, and more preferably alkylene glycol alkyl ether acetates, ketones and ethyl 3-ethoxypropionate. And esters such as methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, and 3-methoxy Methyl propionate etc. are mentioned. These solvents can be used individually or in mixture of 2 or more types, respectively.

Content of the solvent in the blue photosensitive resin composition of this invention can be contained 60-90 mass%, Preferably it is 60-85 mass% with respect to the whole blue photosensitive resin composition containing it. When content of a solvent is the said range, since applicability | paintability tends to be favorable, when apply | coating with coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also called a die coater), and inkjet, it is preferable. .

additive

The blue pattern layer blue photosensitive resin composition which concerns on this invention is a filler, another high molecular compound, a pigment dispersant as needed. Additives, such as an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, can be further included.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively.

As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl peer ether, polyethyleneglycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane , Polyethylenimine, etc., trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), MEGAFAC (manufactured by Dainippon Ink Chemical Industries, Ltd.), Florard (manufactured by Sumitomo 3M), Asahi guard, Surflon (above, manufactured by Asahi Glass), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminoprotriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyl Trimethoxysilane etc. are mentioned. Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

The additives can be used by those skilled in the art as appropriate without departing from the effect of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total blue photosensitive resin composition, but is not limited thereto.

The blue photosensitive resin composition which concerns on this invention can be manufactured, for example by the following method. The scattering particles are mixed with the solvent in advance and dispersed using a bead mill or the like until the average particle diameter becomes 30 to 500 nm. At this time, a dispersing agent can be further used as needed, and some or all of binder resin may be mix | blended. The remaining dispersion of the binder resin, the photopolymerizable compound, the photopolymerization initiator, other components used as necessary, and additional solvents as necessary, are further added to the obtained dispersion (hereinafter sometimes referred to as a mill base) to a predetermined concentration. A desired blue photosensitive resin composition can be obtained.

<Color filter and image display device>

Another aspect of the present invention relates to a color filter comprising a blue pattern layer containing a cured product of the blue photosensitive resin composition for forming a blue pattern layer described above.

Since the color filter according to the present invention is made of the blue photosensitive resin composition for forming the blue pattern layer instead of the blue quantum dots, the manufacturing cost can be lowered and an excellent viewing angle can be obtained.

In addition, by including a photopolymerizable compound containing ethylene oxide or propylene oxide in the blue photosensitive resin composition of the present invention, the color filter including the blue pattern layer prepared using the blue photosensitive resin composition of the present invention controls the development speed In addition, it may be possible to solve the problem caused by the process residue by eliminating the residue of the pattern, to improve the display defect problem, and to implement the color filter, in particular, the self-luminous color filter, which is improved in the problem of the resist undeveloped.

The color filter includes a substrate and a blue pattern layer formed on the substrate.

The substrate may be the substrate of the color filter itself, or may be a portion where the color filter is positioned in a display device or the like, and is not particularly limited. The substrate may be glass, silicon (Si), silicon oxide (SiOx), or a polymer substrate, and the polymer substrate may be polyethersulfone (PES) or polycarbonate (PC).

The blue pattern layer is a layer including the blue photosensitive resin composition of the present invention, and may be a layer formed by applying the blue photosensitive resin composition for forming a blue pattern layer and exposing, developing and thermosetting in a predetermined pattern. Can be formed by carrying out methods commonly known in the art.

In another embodiment of the present invention, the color filter may further include one or more selected from the group consisting of a red pattern layer and a green pattern layer.

In another embodiment of the present invention, the red pattern layer or green pattern layer may include a quantum dot and / or scattering particles. Specifically, the color filter according to the present invention may include a red pattern layer including a red quantum dot or a green pattern layer including a green quantum dot, and the red pattern layer or the green pattern layer may include scattering particles. The red pattern layer or the green pattern layer may emit red light or blue light, respectively, by a light source emitting blue light, which will be described later.

In another embodiment of the present invention, the scattering particles included in the red pattern layer or the green pattern layer may include a metal oxide having an average particle diameter of 30 to 500nm, the details of the scattering particles and the metal oxide The content of the scattering particles and the metal oxide contained in the blue photosensitive resin composition according to the invention can be applied.

In the present invention, the shape, configuration, and content of the quantum dots included in the red pattern layer or the green pattern layer are not limited, and quantum dots commonly used in the art may be applied.

The color filter including the substrate and the pattern layer may further include a partition formed between each pattern, and may further include a black matrix, but is not limited thereto.

In the present invention, the color filter may be a self-luminous color filter.

Another aspect of the invention, the above-described color filter; And a light source emitting blue light. In short, the image display apparatus according to the present invention includes a color filter including a blue pattern layer including a cured product of the above-described blue photosensitive resin composition and a light source emitting blue light.

The color filter of the present invention can be applied to various image display devices such as electroluminescent display devices, plasma display devices, field emission display devices, as well as ordinary liquid crystal display devices.

When the image display device includes a color filter including a blue pattern layer and the light source according to the present invention, there is an advantage of having excellent light emission intensity or viewing angle. In addition, since the blue pattern layer included in the color filter according to the present invention does not include blue quantum dots, there is an advantage in that an image display device having low manufacturing cost can be manufactured.

Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not to be interpreted as being limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art. In addition, "%" and "part" which show content below are a basis of weight unless there is particular notice.

Synthesis Example Synthesis of Binder Resin

Preparation Example 1: Acrylic Alkali Soluble Resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube was prepared, and as the monomer dropping lot, 74.8 g (0.20 mol) of benzylmaleimide, 43.2 g (0.30 mol) of acrylic acid, and vinyltoluene 118.0 g (0.50 mol), 4 g of t-butylperoxy-2-ethylhexanoate and 40 g of propylene glycol monomethyl ether acetate (PGMEA) were added thereto, followed by stirring and mixing. As a chain transfer agent dropping tank, n-dodecanethiol 6g and PGMEA24g were added, and the thing mixed with stirring was prepared. Thereafter, 395 g of PGMEA was introduced into the flask, and the atmosphere in the flask was changed to nitrogen from air, and then the temperature of the flask was raised to 90 ° C. while stirring. Subsequently, dropping of the monomer and the chain transfer agent was started from the dropping lot. The dropwise addition was carried out for 2 h each while maintaining 90 ° C., and after 1 h, the temperature was raised to 110 ° C. and maintained for 3 h. Started. Next, 28.4 g glycidyl methacrylate [(0.10 mol), (33 mol% with respect to the carboxyl group of acrylic acid used for this reaction)], 2,2'- methylenebis (4-methyl-6-t-butylphenol ) 0.4 g and 0.8 g of triethylamine were added to the flask, and the reaction was continued at 110 for 8 hours to obtain a resin A having a solid acid value of 70 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 16,000, and molecular weight distribution (Mw / Mn) was 2.3.

Preparation Example 2 Synthesis of Compound of Formula 1-1-1

364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xantene) and 3-, 6'-dihydroxyspiro (fluorene-9,9-xantene) in a 3000 ml three-neck round flask 0.4159 g of bromide was mixed and 2359 g of epichlorohydrin was added and reacted by heating to 90 ° C. When the 3,6-dihydroxyspiro (fluorene-9,9-xanthene) was completely consumed by liquid chromatography, 50% NaOH aqueous solution (3 equiv) was slowly added by cooling to 30 DEG C. After analysis by liquid chromatography, epichlorohydrin was completely consumed, the mixture was extracted with dichloromethane and washed three times, and then the organic layer was dried over magnesium sulfate. Then dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixture ratio of 50:50.

Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. The temperature was heated to 120 while the reaction solution was cloudy to completely dissolve. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula 1-1-1.

[Formula 1-1-1]

Preparation Example 3 Synthesis of Compound of Chemical Formula 1-1-2

364.4 g of 3 ', 6'-dihydroxyspiro (fluorene-9,9-xanthene) (3', 6 ''-dihydroxyspiro (fluorene-9,9-xantene) of formula 2-1 in a 3000 ml three-neck round flask And 0.4159 g of t-butylammonium bromide were mixed, 2359 g of epichlorohydrin was added and heated to 90 ° C. The reaction was performed by liquid chromatography to analyze 3,6-dihydroxyspiro (fluorene-9,9-xanthene). ) Once completely consumed, cool it to 30 ° C. and slowly add 50% aqueous NaOH solution (3 equiv.) After analyzing by liquid chromatography, epichlorohydrin was completely consumed, extracted with dichloromethane and washed three times, and then the organic layer was washed. After drying over magnesium sulfate, dichloromethane was distilled under reduced pressure and recrystallized using a dichloromethane and methanol mixture ratio of 50:50.

Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid were mixed, and then 24.89 g of a solvent propylene glycol monomethyl ether acetate was added thereto. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula 1-1-2.

[Formula 1-1-2]

Preparation Example 4 Synthesis of Compound of Chemical Formula 1-2-1

34.4 g of 4,4 '-(9H-xanthene-9,9-diyl) diphenol and 3-butylammonium bromide in a 3000 ml three-neck round flask 0.4159g was mixed, 2359g of epichlorohydrin was added and heated to 90 to react. By liquid chromatography, 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenol) is completely depleted and cooled to 30 ℃. 50% NaOH aqueous solution (3 equiv) was added slowly. After epichlorohydrin was completely exhausted by liquid chromatography, the mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled under reduced pressure, and the mixture ratio of dichloromethane and methanol was 50:50. Recrystallized. Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol and 2.2 equivalent of acrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added thereto and mixed. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula 1-2-1.

[Formula 1-2-1]

Preparation Example 5 Synthesis of Compound of Formula 1-2-2

34.4 g of 4,4 '-(9H-xanthene-9,9-diyl) diphenol and 3-butylammonium bromide in a 3000 ml three-neck round flask 0.4159 g was mixed, 2359 g of epichlorohydrin was added, and the mixture was heated and reacted at 90 ° C. By liquid chromatography, 4,4 '-(9H-xanthene-9,9-diyl) diphenol (4,4'-(9Hxanthene-9,9-diyl) diphenol) is completely depleted and cooled to 30 ℃. 50% NaOH aqueous solution (3 equiv) was added slowly. After epichlorohydrin was completely exhausted by liquid chromatography, the mixture was extracted with dichloromethane and washed three times. The organic layer was dried over magnesium sulfate, and dichloromethane was distilled under reduced pressure, and the mixture ratio of dichloromethane and methanol was 50:50. Recrystallized. Thus, 1 equivalent of the epoxy compound, 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalent of methacrylic acid were mixed, and then 24.89 g of solvent propylene glycol monomethyl ether acetate was added and mixed. The temperature was melt | dissolved by heating at 90-100 degreeC, blowing air into this reaction solution at 25 ml / min. In the state where the reaction solution was cloudy, the temperature was heated to 120 ° C. to completely dissolve it. When the solution became clear and the viscosity became high, the acid value was measured and stirred until the acid value was less than 1.0 mgKOH / g. It took 11 hours to reach the target (0.8). After completion of the reaction, the temperature of the reactor was lowered to room temperature to obtain a colorless transparent compound of formula 1-2-2.

[Formula 1-2-2]

Preparation Example 6 Synthesis of Cardo-Based Binder Resin (A-1)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of Formula 1-1-1 of Preparation Example 2, 78 g of biphenyl tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed up to 110 The reaction was carried out at ˜115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize with a cardo binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 3500

Preparation Example 7 Synthesis of Cardo-Based Binder Resin (A-2)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of Formula 1-1-2 of Preparation Example 3, 78 g of biphenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed up. The reaction was carried out at ˜115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize with a cardo binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 3800

Preparation Example 8 Synthesis of Cardo-Based Binder Resin (A-3)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of Formula 1-2-1 of Preparation Example 4, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed up to 110 to The reaction was carried out at 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize with a cardo binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 4500

Preparation Example 9 Synthesis of Cardo-Based Binder Resin (A-4)

After dissolving 600 g of propylene glycol monomethyl ether acetate in 307.0 g of the compound of formula 1-2-2 of Preparation Example 5, 78 g of phenyltetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually warmed up to 110 ~. The reaction was carried out at 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to polymerize with a cardo binder resin. Loss of anhydride was confirmed by IR spectrum. Weight average molecular weight: 4900

Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)

Column temperature: 40 ℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Sample concentration measured: 0.6 wt% (solvent = tetrahydrofuran)

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).

Examples 1 to 9 Comparative Examples 1 to 7: Preparation of Blue Photosensitive Resin Compositions

To the blue photosensitive resin composition of Examples 1 to 9 Comparative Examples 1 to 3 according to the composition of Tables 1 to 3. (Table 1 shows scattering particles, and Table 2 shows the composition and content of the compositions of Examples and Comparative Examples.)

TABLE 1

TABLE 2

Manufacture of color filter

Color filters were prepared using the metal oxide photosensitive resin compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 7. That is, each of the photosensitive resin composition was applied on a glass substrate by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C. for 3 minutes to form a thin film.

Subsequently, a test photomask having a transmissive pattern of 20 mm x 20 mm square and a line / space pattern of 1 to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask.

At this time, the ultraviolet light source was irradiated with an exposure amount (365 nm) of 200 mJ / cm 2 under an atmospheric atmosphere using an ultra high pressure mercury lamp (trade name USH-250D) manufactured by Ushio Denki Co., Ltd., and no special optical filter was used.

The thin film irradiated with ultraviolet rays was developed by soaking for 80 seconds in a KOH aqueous solution developing solution of pH 10.5. The thin film coated glass plate was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 150 ° C. for 10 minutes to prepare a color filter pattern. The film thickness of the color pattern prepared above was 5.0 μm.

Experimental Example 1: Development speed, sensitivity, pattern stability, taper line width and shape of color filter

The color filters prepared from the blue photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated as shown in Table 3 below. Evaluation criteria for each experiment are as follows.

Development speed (sec): Time taken for the first non-exposure part to dissolve in the developer during development <Spray Developer HPMJ method>

Sensitivity: The degree of formation of a flawless thin film of the sensitivity mask fine pattern (1 to 60) (the lower the value, the better the sensitivity).

Pattern Stability: Pattern error after exposure of pattern mask at low exposure amount (20-100mJ)

○: no error on the pattern

X: 3 or more errors on the pattern

○, X is the result confirmed by the optical microscope of the three-dimensional surface shaper.

Tapered line width (µm): Post-exposure line width of 100 µm pattern of pattern mask.

TABLE 3

If the developing speed exceeds 60 seconds, it is impossible to manufacture within a given process time, and if it exceeds 30 seconds, the roughness of the pattern surface becomes uneven and uniformity may also be reduced. In Examples 1 to 5 of the present invention, the development speed was less than 30 seconds, and the sensitivity was less than 60, and it was confirmed that the pattern stability and the taper line width had excellent effects. On the other hand, in Comparative Example 1, the scattering particles are not included, the pattern stability is unstable, causing an imbalance of the pattern. In the case of Comparative Example 2, when combined with only acrylic resin, the scattering particles and the blue colorant could not be supported as strongly as the cardo-based binder resin, and thus peeled off, and in Comparative Example 3, photopolymerizable without ethylene oxide and propylene oxide In the case of the compound, the development speed was significantly decreased, and the long development speed confirmed that pattern stability and pattern imbalance occurred.

Experimental Example 2 Fine Pattern Measurement

The size of the pattern obtained through the line / space pattern mask designed to 100 μm of the color filters manufactured using the metal oxide photosensitive resins prepared in Examples 1 to 5 and Comparative Examples 1 to 3 was obtained by OM equipment (ECLIPSE LV100POL Nikon). G) through the pattern size was measured, the results are shown in Table 4 below.

TABLE 4

If the difference between the design value of the line / space pattern mask and the measured value of the obtained fine pattern is 20 µm or more, it is difficult to implement the fine pixel.

As can be seen in Table 4, in Examples 1 to 4 including a photopolymerizable compound to which ethylene oxide and propylene oxide were added, it was confirmed that a micropattern of less than 20 μm was formed. On the other hand, in the case of Comparative Examples 1 to 3 it was confirmed that the fine pattern is poorly formed or peeled off to determine whether the pattern is formed.

Experimental Example 3 Measurement of Luminescence Intensity

365 nm tube type 4 W UV irradiator (VL-4LC) on the portion formed in the pattern of 20 x 20 mm square of the color filter prepared using the metal oxide photosensitive resin prepared in Examples 1 to 5 and Comparative Examples 1 to 3 , VILBER LOURMAT) was used to measure the light conversion region, and Examples 1 to 5 and Comparative Examples 1 to 3 measured the emission intensity in the 450 nm region using a Spectrum meter (Ocean Optics). The results are shown in Table 5 below.

TABLE 5

The higher the measured light emission intensity, the higher the light efficiency. In Table 6, it can be seen that in Examples 1 to 5 including the photopolymerizable compound to which ethylene oxide and propylene oxide were added, the emission intensity was improved to 3 or more. On the other hand, in Comparative Examples 1 to 3 it was confirmed that the light efficiency was lowered to 2 or less.

Experimental Example 4 Viewing Angle Measurement

An optical intensity according to the viewing angle under light transmission conditions in a portion of a color filter manufactured using the metal oxide photosensitive resin prepared in Examples 1 to 5 and Comparative Examples 1 to 3 in a pattern of 20 x 20 mm square. It was measured using (GC-5000L, Nippon Denshoku), and the diffusion rate was calculated using the following equation 1.

[Equation 1]

Diffusion rate = (B ₇₀ + B ₂₀ ) / 2 x B ₅ x 100

(B _θ = I _θ / cosθ)

I means light intensity measured at each angle, and means measured at B _70, B _20, B ₅ 70 degrees, 20 degrees and 5 degrees.

TABLE 6

The higher the measured diffusion, the better the viewing angle. In Table 7, Examples 1 to 5 including the photopolymerizable compound added with ethylene oxide and propylene oxide had a diffusion ratio of 85 or more, and it was confirmed that the viewing angle was very excellent. On the other hand, in Comparative Examples 1 and 3, the diffusion rate was remarkably dropped compared to Examples 1 to 5, and it was confirmed that the diffusion angle could not be measured because the viewing angle was lowered or peeled off.

The present invention includes a photopolymerizable compound containing alkylene oxide in the blue photosensitive resin composition, to control the development speed, solve the problem caused by the process residue by eliminating the residue of the pattern, and poor display problems are improved In addition, the present invention provides a color filter in which the problem of resist non-developing is improved. In addition, it is possible to provide a high-quality self-luminous color filter having an excellent viewing angle by adjusting the taper.

Claims (16)

A blue photosensitive resin composition comprising a scattering particle, a blue colorant, a photoinitiator, and a photopolymerizable compound including a cardo-based binder resin as a binder resin and an alkylene oxide as a photopolymerizable compound, The photopolymerizable compound is a blue photosensitive resin composition, characterized in that it comprises a photopolymerizable compound comprising an alkylene oxide. The method according to claim 1, The scattering particles are blue photosensitive resin composition comprising a metal oxide having an average particle diameter of 10 to 1000nm. The method according to claim 1, The scattering particles are selected from the group consisting of Al ₂ O ₃ , SiO ₂ , ZnO, ZrO ₂ , BaTiO ₃ , TiO ₂ , Ta ₂ O ₅ , Ti ₃ O ₅ , ZnO, Nb ₂ O ₃ , SnO and MgO A blue photosensitive resin composition containing species or more. The method according to claim 1, The said blue photosensitive resin composition is a blue photosensitive resin composition which further contains a purple coloring agent. The method according to claim 1, The blue photosensitive resin composition is a blue photosensitive resin composition further comprising a photopolymerizable compound that does not contain an alkylene oxide. The method according to claim 1, And the blue colorant comprises at least one of a blue pigment and a blue dye. The method according to claim 1, The cardo-based binder resin is a blue photosensitive resin composition comprising one or more of the compounds represented by the following formula 1-1 and formula 1-2: [Formula 1-1]

[Formula 1-2]

(In Formula 1-1 or Formula 1-2, R ₁ , R ₂ , R ₃ and R ₄ are each independently,

Is; X is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group; R ₅ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.). The method according to claim 1, The cardo-based binder resin may be a resin of 9,9-bis (3-cinnamic diester) fluorene (9,9-bis (3-cinnamic diester) fluorene), 9,9-bis (3-cinamoyl, 4 -Hydroxyphenyl) fluorene (9,9-bis (3-cinnamoil, 4-hydroxyphenyl) fluorene), 9,9-bis (glycidyl methacrylate ether) fluorene (9,9-bis (glycidyl methacrylate) ether) fluorene), 9,9-bis (3,4-dihydroxyphenyl) fluorene disinmic ester (9,9-bis (3,4-dihydroxyphenyl) fluorene dicinnamic ester), 3,6-diglyci Dyl methacrylate ether spiro (fluorene-9,9-xanthene) (3,6-diglycidyl methacrylate ether spiro (fluorene-9,9-xantene)), 9,9-bis (3-allyl, 4-hydroxy Phenylfluorene) (9,9-bis (3-allyl, 4-hydroxyphenlylfluorene), 9,9-bis (4-allyloxyphenyl) fluorene (`9,9-bis (4-allyloxyphenyl) fluorene) and 9 And at least one member selected from the group consisting of 9-bis (3,4-methacrylic diester) fluorene (9,9-bis (3,4-methacrylic diester) fluorine). It is a blue photosensitive resin composition. The method according to claim 1, The blue photosensitive resin composition, wherein the blue photosensitive resin composition further comprises an acrylic alkali-soluble resin as a binder resin. The method according to claim 1, The photopolymerizable compound including the alkylene oxide is ethylene oxide modified trimetholpropane triacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, ethylene oxide modified pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol tetra Acrylate, propylene oxide modified pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated pentaerythritol polyacrylate, propoxylated diacrylate The blue photosensitive resin composition which is at least 1 type selected from the group which consists of pentaerythritol hexaacrylate and an ethoxylated glycerine triacrylate. The method according to claim 1, 0.1 to 50% by weight of scattering particles based on the total weight of solids in the blue photosensitive resin; 0.1 to 50% by weight blue colorant; 5 to 85% by weight of binder resin; 5-50% by weight of the photopolymerizable compound; 0.1-30% by weight of photoinitiator; And 0.001 to 10% by weight of a UV absorber comprising at least one of the benzotriazole-based, triazine-based and benzophenone-based, comprising a solvent 60 to 90% by weight relative to the total weight of the blue photosensitive resin composition, blue Photosensitive resin composition. The color filter containing the blue pattern layer which consists of a blue photosensitive resin composition of any one of Claims 1-11. The method according to claim 12, The color filter further comprises one or more selected from the group consisting of a red pattern layer and a green pattern layer. The method according to claim 13, The red pattern layer or the green pattern layer is a color filter comprising a quantum dot. The method according to claim 14, The color filter is a color filter, characterized in that the self-luminous color filter. A color filter according to claim 12; And A light source emitting blue light; Image display device comprising a.