TW201937285A - Colored photosensitive resin composition, color filter including black matrix, column spacer or black column spacer manufactured using the colored photosensitive resin composition, and display device including the color filter - Google Patents

Abstract

This invention relates to a colored photosensitive resin composition including a colorant including an organic black pigment, a violet pigment and a blue pigment, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator and a solvent, to a color filter including a black matrix, a column spacer or a black column spacer manufactured using the colored photosensitive resin composition, and to a display device including the color filter.

Description

Coloring the photosensitive resin composition, including using a colored photosensitive resin composition Color filters made of black matrix, column spacers or black column spacers, and color filters included Light display device

The present invention relates to a colored photosensitive resin composition, a color filter including a black matrix, a pillar spacer or a black pillar spacer produced using the colored photosensitive resin composition, and a display device including the color filter.

The color filter can be used for actual acquisition by being embedded in an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge-coupled device (CCD), or the like. Color image. In addition, color filters are widely used in imaging devices, plasma display panels (PDPs), liquid crystal displays (LCDs), field emission displays (FELs), and light-emitting displays (light- Cover display, LED), etc., and its application range is rapidly expanding. In particular, more and more cases have recently been used for liquid crystal displays, and thus color filters are considered to be one of the most important components for reproducing the color of liquid crystal displays.

The color filter is manufactured by coating a colored photosensitive resin composition containing a coloring agent corresponding to each of red, green, and blue uniformly onto a patterned black matrix thereon by spin coating. The substrate is then heated and dried (hereinafter referred to as "prebaking") to form a coating film, which is then exposed and developed, and may be additionally heat-hardened as needed (hereinafter referred to as "post-baking"). And repeating the steps for each color to form individual color pixels. Recently, as display sizes have rapidly increased and continuous high contrast has been required, a process using dyes or simultaneous dyes and pigments has been used to color the photosensitive resin composition in place of the conventional pigment dispersion process. Although a dye having a high light transmittance can be provided when the coloring photosensitive resin composition uses a dye for producing a color filter and when the coloring photosensitive resin composition uses both a dye and a pigment for use in manufacturing a mixed color filter. Color filters, but depending on the type of dye used and the photoinitiator, the sensitivity may be reduced. Therefore, intensive research is being conducted to prevent the sensitivity of the color filter from being lowered by solving the above problem.

Korean Patent No. 10-0529638 discloses a photopolymerizable resin composition containing N-phenylglycine and a triazine compound as a starter, and thus exhibits excellent resolution and pattern. Adhesion, development margin, and surface and internal hardness, but insufficient improvement in solvent resistance and optical density.

[cited literature]

[Patent Literature]

Korean Patent No. 10-0529638

Accordingly, the present invention is directed to providing a colored photosensitive resin composition which is colored The photosensitive resin composition can exhibit excellent optical density and low-temperature reactivity and thus has an improved hardness, thereby exhibiting high reliability such as solvent resistance and chemical resistance.

Further, the present invention is directed to a color filter including a black matrix, a pillar spacer or a black pillar spacer manufactured using the colored photosensitive resin composition, and a display device including the color filter.

Accordingly, the present invention provides a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises an organic black pigment, a blue pigment and a violet pigment, and the alkali-soluble resin comprises a copolymer of the following Chemical Formula 1 or Chemical Formula 2:

Wherein (A) is 3,4-epoxycyclohexylmethyl (meth)acrylate, 4-methylpropenyloxyethyl trimellitic anhydride or hydroxyethyl methacrylate, and in Chemical Formula 1, monomer a and single The molar ratio of the body b is 2:8 to 9:1, and in the chemical formula 2, the monomer a, the monomer b and the monomer c The ratio is 2:3:5 to 8:1:1.

Further, the present invention provides a color filter comprising a black matrix, a column spacer or a black column spacer manufactured using the colored photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

According to the present invention, the colored photosensitive resin composition can exhibit excellent optical density and low-temperature reactivity, as well as high reliability such as solvent resistance and chemical resistance.

Further, the color filter and the display device manufactured using the colored photosensitive resin composition of the present invention can realize highly accurate color reproduction.

Hereinafter, the present invention will be described in detail.

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises an organic black pigment, blue a color pigment and a purple pigment, and the alkali-soluble resin contains a copolymer of the following Chemical Formula 1 or Chemical Formula 2:

[Chemical Formula 2]

Wherein (A) is 3,4-epoxycyclohexylmethyl (meth)acrylate, 4-methylpropenyloxyethyl trimellitic anhydride or hydroxyethyl methacrylate.

In Chemical Formula 1, the molar ratio of monomer a to monomer b is from 2:8 to 9:1.

In Chemical Formula 2, the molar ratio of the monomer a, the monomer b to the monomer c is 2:3:5 to 8:1:1.

In the present invention, the colorant includes an organic black pigment, a violet pigment, and a blue pigment, thereby improving the optical density of the colored photosensitive resin composition, and the alkali-soluble resin includes the copolymer of Chemical Formula 1 or Chemical Formula 2, thereby improving coloring. The low-temperature reactivity of the photosensitive resin composition and also the reliability, such as solvent resistance and chemical resistance, are also improved by the crosslinking reaction.

The components of the colored photosensitive resin composition according to the present invention will be described in detail below.

(A) colorant

In the present invention, a coloring agent capable of blocking visible light is used, and the coloring agent of the present invention includes an organic black pigment, a purple pigment, and a blue pigment.

The organic black pigment includes at least one selected from the group consisting of indoleamine black, aniline black, and phthalocyanine, and more specifically, 100CF (manufactured by BASF Corporation). When an organic black pigment is contained, the optical density can be improved without affecting the infrared range, and the dielectric constant and light transmittance can be improved.

The purple pigment is used to reduce the light transmittance in the wavelength range of 400 nm to 600 nm, thereby increasing the optical density (O.D.). Reduce the amount of organic black required by using purple pigment Since the amount of the material is increased, the reliability of the colored photosensitive resin composition can be improved. The type of the purple pigment is not particularly limited, and preferably includes at least one selected from the group consisting of CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 31, and CI Pigment Violet 37. CI Pigment Violet 29 was used.

Blue pigments are compounds that do not contain a central metal. The presence of the central metal may affect the driving of the liquid crystal, so the present invention uses a compound containing no central metal as the blue pigment, thereby enabling efficient operation of the device. In the present invention, the kind of the blue pigment is not particularly limited as long as it does not contain a central metal, and is preferably composed of selected from CI Pigment Blue 16, CI Pigment Blue 60, CI Pigment Blue 63, and CI Pigment Blue 66. At least one of the groups, CI Pigment Blue 60 is optimally used.

In the present invention, the content of the colorant is from 13% by weight to 60% by weight, based on the total weight of the solid content of the colored photosensitive resin composition, and preferably from 25% by weight to 45% by weight. When the amount of the colorant is from 13% by weight to 50% by weight, excellent optical density and reliability can be obtained.

More specifically, the colorant includes an organic black pigment, a violet pigment, and a blue pigment which are mixed in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3 and preferably in a weight ratio of 1:0.27 to 1:0.47 to 2.25.

When the organic black pigment is contained in the above weight ratio, a colored photosensitive resin composition having excellent optical density and reliability can be obtained. Further, the amount of the organic black pigment is from 6% by weight to 25% by weight, and preferably from 8% by weight to 15% by weight, based on the total weight of the solid content of the colored photosensitive resin composition.

When the violet pigment is contained in the above weight ratio, a colored photosensitive resin composition having excellent optical density and reliability can be obtained. In addition, the solidification of the photosensitive photosensitive resin composition The amount of the violet pigment is from 2% by weight to 15% by weight, and preferably from 4% by weight to 8% by weight, based on the total weight of the body content.

When the blue pigment is contained in the above weight ratio, a colored photosensitive resin composition having an excellent optical density can be obtained. Further, the amount of the blue pigment is from 5% by weight to 20% by weight, and preferably from 7% by weight to 18% by weight, based on the total weight of the solid content of the colored photosensitive resin composition.

Further, the coloring agent of the colored photosensitive resin composition of the present invention may further contain carbon black. When the colorant further comprises carbon black, the organic black pigment, the violet pigment, the blue pigment and the carbon black of the colorant may be mixed in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3:0.12 to 1.7, and preferably 1:0.27 to 1:0.47 to 1.88: 0.27 to 0.87 by weight mixing. Here, the content of the carbon black is from 3% by weight to 10% by weight, and preferably from 4% by weight to 7% by weight, based on the total weight of the solid content of the colored photosensitive resin composition.

When carbon black is contained in the above weight ratio range, a colored photosensitive resin composition having an excellent optical density can be obtained.

In the present invention, the solid content of the colored photosensitive resin composition means the sum of components other than the solvent.

Further, the colorant is preferably used in the form of a pigment dispersion solution in which the pigment particles are uniformly dispersed. The process of uniformly dispersing the pigment particles may include, for example, a dispersion treatment process using a pigment dispersant (a1) or the like, and according to this process, a pigment dispersion solution in which the pigment is uniformly dispersed in a solution can be obtained.

(a1) pigment dispersant

Adding a pigment dispersant to prevent pigment aggregation and maintain its stability, and pigment Specific examples of the dispersing agent may include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyester surfactant, a polyamine surfactant, and the like, and the surfactants may be used alone. Use or in combination of two or more thereof.

Specific examples of the cationic surfactant may include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride and quaternary ammonium salts.

Specific examples of the anionic surfactant may include higher alcohol sulfate salts such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; and alkylarylsulfonates Acid salts such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene/oxypropylene block copolymer, Sorbitol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Other examples may include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyamines Formate and polyethyleneimine.

Further, the pigment dispersant preferably includes an acrylate-based dispersant comprising butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) (hereinafter referred to as "acrylate dispersion" Agent"). The acrylate-based dispersing agents preferably include those prepared by a living control process, and commercially available products thereof may include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150. These acrylate-based dispersants may be used singly or in combination of two or more thereof.

In addition to the acrylate dispersant, the pigment dispersant may include another resin Type pigment dispersant. Another resin type pigment dispersant may include known resin type pigment dispersants, particularly oily dispersants such as polycarboxylates (such as polyurethanes or polyacrylates), unsaturated polyamines, and polycarboxylates. Acid, poly(carboxylic acid) (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine salt, polyoxyalkylene oxide, long-chain polyamine guanamine phosphate, hydroxyl group-containing polycarboxylate And a modified product thereof, or a guanamine or salt formed by the reaction of a polyester having a free carboxyl group with a poly(lower alkylene imine); a water-soluble resin or a water-soluble polymer compound such as (methyl) Acrylic-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; polyester; modified polyacrylic acid Ester; an adduct of ethylene oxide/propylene oxide; and a phosphate ester.

Commercially available products of other resin type pigment dispersants may include cationic resin dispersants such as those available from BYK Chemie under the following trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK- 162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, and DISPER BYK-184; products available from BASF under the following trade names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA- 4406, EFKA-4510, and EFKA-4800; available from Lubrizol under the trade names: SOLSPERS-24000, SOLSPERS-32550, and NBZ-4204/10; available from Japan Chuanyan Fine Chemicals Kawaken Fine Chemicals has obtained the following trade names: HINOACT T-6000, HINOACT T-7000 and HINOACT T-8000; products available from Ajinomoto under the following trade names: AJISPUR PB -821, AJISPUR PB-822 and AJISPUR PB-823; and products available under the trade names of Kyoeisha Chemical: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. .

These other resin type pigment dispersants may be used singly or in combination of two or more thereof in addition to the acrylate-based dispersant, and may be used together with the acrylate-based dispersant.

The amount of the pigment dispersant is 1 part by weight or less but more than 0 part by weight, and preferably 0.05 part by weight to 0.5 part by weight, based on 1 part by weight of the coloring agent. When the amount of the pigment dispersant is 1 part by weight or less but more than 0 part by weight, a uniformly dispersed pigment can be obtained.

(B) alkali soluble resin

The alkali-soluble resin generally makes the unexposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition alkali-soluble, and an adhesive resin as a colorant or a dispersion medium thereof.

In order to manufacture a color filter, the alkali-soluble resin includes an alkali-soluble resin which is soluble in an alkaline developing solution during development, and the alkali-soluble resin of the present invention includes a copolymer of the following Chemical Formula 1 or Chemical Formula 2.

[Chemical Formula 2]

Wherein (A) is 3,4-epoxycyclohexylmethyl (meth)acrylate (CYM-M100, manufactured by Daicel), hydroxyethyl methacrylate (HEMA) and/or 4-methyl Propylene oxiranyl ethyl trimellitic anhydride (4-META).

In Chemical Formula 1, the molar ratio of monomer a to monomer b is 2:8 to 9:1, and in Chemical Formula 2, the molar ratio of monomer a, monomer b to monomer c is 2:3 : 5 to 8:1:1.

In the present invention, the alkali-soluble resin includes a copolymer having an epoxy group as shown in Chemical Formula 1 or Chemical Formula 2, thereby improving the low-temperature reactivity of the colored photosensitive resin composition and improving the hardness by the crosslinking reaction, and finally improving the reliability. Sex, such as solvent resistance and chemical resistance.

The weight average molecular weight of the alkali-soluble resin falls within the range of 3,000 to 20,000, and preferably 5,000 to 15,000.

Further, the acid value of the alkali-soluble resin falls within the range of 50 mg KOH/g to 200 mg KOH/g in terms of solid content. Within the above range, developability at the time of alkaline development can be made high, development residue can be prevented from occurring, and pattern adhesion can be improved.

The alkali-soluble resin may be a copolymer of at least one selected from the group consisting of Chemical Formula 1 and Chemical Formula 2 and another monomer copolymerizable therewith.

The amount of the alkali-soluble resin is from 5% by weight to 60% by weight, and preferably from 20% by weight to 50% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. When the amount of the alkali-soluble resin falls within the above range, the pattern is easily formed, and the resolution and the ratio of the remaining film can be improved. Rate, this is better.

(C) Photopolymerizable compound

The photopolymerizable compound containing an unsaturated bond and photoreactive with a photoinitiator to form a colored photosensitive resin layer is a compound which can be polymerized under the action of a photoinitiator (D) which will be described later.

In the present invention, the functional group of the photopolymerizable compound may be a generally useful (meth) acrylate.

The photopolymerizable compound contains 3 to 10 functional groups, preferably 4 to 8 functional groups.

Among the polyfunctional monomers, specific examples of the trifunctional monomer may include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylation Trimethylolpropane tri(meth)acrylate and neopentyl alcohol tri(meth)acrylate.

Among the polyfunctional monomers, specific examples of the tetrafunctional monomer may include neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, bis(trimethylolpropane) tetraacrylate, and di(trishydroxyl). Methyl propane) tetramethacrylate, dipentaerythritol tetraacrylate, tetramethylol methane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerol tetraacrylate and glycerol tetramethacrylate ester.

Among the polyfunctional monomers, specific examples of the pentafunctional monomer may include dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol monohydroxypentaacrylate, dioxane Tetraol monohydroxypentamethacrylate and the like.

Among the polyfunctional monomers, specific examples of the hexafunctional monomer may include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like.

In the polyfunctional monomer, specific examples of the heptafunctional to decafunctional monomer may include three Pentaerythritol octa methacrylate, tripentenol octaacrylate, tetrapentaerythritol heptamethacrylate, and tetrapentaerythritol heptaacrylate.

The amount of the photopolymerizable compound is from 5% by weight to 50% by weight, and preferably from 7% by weight to 45% by weight, based on the total weight of the solid content of the colored photosensitive resin composition of the present invention. When the amount of the photopolymerizable compound falls within the range of 5 to 50% by weight, the intensity or smoothness of the pixel portion may be good.

Further, in the present invention, the alkali-soluble resin and the photopolymerizable compound are mixed in a weight ratio of 1:1 to 5:1, and preferably 1.2:1 to 3.7:1. When the alkali-soluble resin and the photopolymerizable compound are mixed in a weight ratio of 1:1 to 5:1, a colored photosensitive resin composition characterized by improved workability and increased ease of pattern formation can be provided.

(D) Photoinitiator

The photoinitiator can be used without limitation as long as it can polymerize the photopolymerizable compound, and it is preferable to select a acetophenone-based compound from the viewpoint of polymerization characteristics, initial efficiency, absorption wavelength, commercial availability, price, and the like. At least one compound of the group consisting of a benzoin-based compound, a benzophenone-based compound, a triazine-based compound, a diimidazole-based compound, an anthraquinone-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone-based compound may include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1 -[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl) -2-Folinin propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-hydroxy-2- Methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4) -Folininylphenyl)butan-1-one.

Specific examples of the benzoin-based compound may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the benzophenone-based compound may include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl Thioether, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Specific examples of the triazine-based compound may include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloro) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2- (3,4-Dimethoxyphenyl)vinyl]-1,3,5-triazine.

Specific examples of the diimidazole-based compound may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-dichlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2'-double (2,6-Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and its phenyl group at the 4,4',5,5' position An alkoxycarbonyl substituted imidazole compound.

More preferably, examples thereof may include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2-bis(2,6-dichlorophenyl)-4,4',5,5'-tetraphenyl -1,2'-biimidazole and the like.

Specific examples of the lanthanoid compound may include o-ethoxycarbonyl-α-oxyimino-1- Phenylpropan-1-one and the like, and commercially available products thereof include OXE01 and OXE02 manufactured by BASF Corporation.

Specific examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythiophene. Tons of ketone and so on.

The photoinitiators may be used singly or in combination of two or more thereof.

In the present invention, the amount of the photoinitiator is from 0.1% by weight to 40% by weight, based on the total weight of the solid content of the colored photosensitive resin composition, and preferably from 1% by weight to 30% by weight.

When the amount falls within the range of 0.1% by weight to 40% by weight, the colored photosensitive resin composition is highly sensitive, and therefore the strength and surface smoothness of the pixel portion formed using the colored photosensitive resin composition can be made excellent.

Further, in the present invention, a photoinitiator aid may be used in addition to the photoinitiator.

The photoinitiator aid is a compound for promoting the polymerization of the photopolymerizable compound, and the photopolymerization of the photopolymerizable compound is initiated by a photoinitiator. Examples of the photoinitiator auxiliary may include an amine compound and an alkoxy fluorene compound.

Specific examples of the amine compound may include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-(Dimethylamino)benzophenone (ie Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-double (ethylmethylamino) benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferably used.

Specific examples of the alkoxy ruthenium compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl -9,10-diethoxyanthracene.

Further, a commercially available photoinitiator auxiliary can be used, and an exemplary commercially available photoinitiator auxiliary is "EAB-F" (manufactured by Hodogaya Chemical Co., Ltd.) .

When a photoinitiator aid is used in this manner, the amount of photoinitiator aid is 10 moles or less, but more than 0 moles, and preferably 0.01, for 1 mole of photoinitiator. Moor to 5 moles. When the amount of the photoinitiator auxiliary is 10 mol or less but exceeds 0 mol, the sensitivity of the colored photosensitive resin composition is further improved, and color filter formed using the colored photosensitive resin composition can be improved The productivity of the film.

(E) solvent

As the solvent, any solvent which is generally used in the field of coloring the photosensitive resin composition can be used as long as it is effective for dissolving the components of the colored photosensitive resin composition, and is not particularly limited, and examples thereof preferably include ether, B. Acid esters, aromatic hydrocarbons, ketones, alcohols and esters.

Examples of the ether may include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; and diethylene glycol dialkyl ether For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetate may include methylcellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, lactic acid. Butyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol Acetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, ethyl 3-methoxy-1-butyrate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether Acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether Acid ester, diethylene glycol monoacetate, diethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, carbonic acid extension Ethyl ester and propyl carbonate.

Examples of the aromatic hydrocarbon may include benzene, toluene, xylene, and mesitylene.

Examples of the ketone may include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Examples of the alcohol may include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and 4-hydroxy-4-methyl-2-pentanone.

Examples of the ester may include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and γ-butyrolactone.

These solvents may be used singly or in combination of two or more thereof.

The solvent is preferably an organic solvent having a boiling point of from 100 ° C to 200 ° C, and examples thereof may include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3, in view of easiness of coating and drying. Ethyl ethoxypropionate and methyl 3-methoxypropionate.

The amount of the solvent is from 60% by weight to 90% by weight, based on the total weight of the colored photosensitive resin composition, and preferably from 65% by weight to 85% by weight. When the amount of the solvent falls within the range of 60% by weight to 90% by weight, a coating device such as a roll coater, a spin coater, a slit spin coater, a slit spin coater (or a die coater) may be used. Or the composition is applied by an inkjet coater, whereby the coatability can be improved.

(F) additive

In addition to the above components, the colored photosensitive resin composition of the present invention may contain an additive within a range not inhibiting the object of the present invention, as required by those skilled in the art.

Specifically, it is selected from another polymer compound, a thermal initiator, a curing agent, At least one additive of the group consisting of a surfactant, an adhesion promoter, an antioxidant, a UV absorber, and a cohesion inhibitor may be further included. In the present invention, a hot initiator is preferably included as an additive.

Specific examples of the additional polymer compound may include curable resins such as epoxy resins and maleic imine resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. Esters, polyesters and polyurethanes.

The role of the thermal initiator is to maximize the initial efficiency by causing a curing reaction with heat. The thermal initiator can be a peroxide compound.

Specifically, the kind of the hot initiator is not particularly limited, but may include at least one selected from the group consisting of tetramethylbutyl peroxy neodecanoate (for example, Perocta ND, NOF) , bis(4-butylcyclohexyl)peroxydicarbonate (for example, Peroyl TCP, manufactured by Enfu), bis(2-ethylhexyl)peroxycarbonate, butyl peroxy neodecanoate For example, Perbutyl ND (manufactured by Enfu), dipropyl peroxydicarbonate (for example, Peroyl NPP, manufactured by Enfu), diisopropyl peroxydicarbonate (for example, Peroyl IPP, manufactured by Enfu), Diethoxyethyl peroxydicarbonate (for example, Peroyl EEP, manufactured by Enfu), diethoxyhexyl peroxydicarbonate (for example, Peroyl OEP, manufactured by Enfu), hexyl peroxydicarbonate (eg Perhexyl ND, manufactured by Enfu), dimethoxybutyl peroxydicarbonate (eg Peroyl MBP, manufactured by Enfu), bis(3-methoxy-3-methoxybutyl) Peroxydicarbonate (Peroyl SOP, manufactured by Enfu), dibutyl peroxydicarbonate, dicetyl peroxydicarbonate, dicumin peroxide Oxime ester, 1,1,3,3-tetramethylbutyl peroxypivalate, peroxypivalate (eg Perhexyl PV, manufactured by Enfu), butyl peroxypivalate (eg Perbutyl) , by Eofu Co., Ltd.), trimethyl hexanoyl peroxide (eg Peroyl 355, manufactured by Enfu), dimethyl hydroxybutyl phthalate (eg Luperox 610M75, manufactured by Atofina), amyl peroxy neodecanoate (eg Luperox 546M75) , manufactured by Atofina Co., Ltd., butyl peroxy neodecanoate (eg Luperox 10M75, manufactured by Atofina), tert-butyl peroxy neoheptanoate, amyl peroxypivalate (eg Luperox 546M75) , made by Atofina, third butyl peroxypivalate, third amyl peroxy-2-ethylhexanoate, lauryl peroxide, dilaurin peroxide, over Dioxin, benzammonium peroxide, benzamidine peroxide, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)cyclohexane , 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis(t-butylperoxy)-1-methylethylbenzene, 1,1 - bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, Tert-butyl peroxy isopropyl carbonate, isophenylene hydroperoxide Bis iso-phenylpropyl peroxide (dicumyl peroxide), acyl lauroyl peroxide (lauroyl peroxide), 2,4- pentanedione peroxide, tertiary butyl peracetic acid, peracetic acid and potassium persulfate.

The amount of the hot starter is from 1% by weight to 10% by weight, and preferably from 1% by weight to 5% by weight, based on the total weight of the solid content of the colored photosensitive resin composition. Within the above range, workability and undercut become better.

The curing agent is used to achieve core curing and high mechanical strength, and specific examples thereof may include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent may include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, Other aromatic epoxy resins, alicyclic epoxy resins, glycidyl ester resins, glycidylamine resins, bromide derivatives of epoxy resins, and aliphatic groups in addition to epoxy resins and their bromide derivatives , alicyclic or aromatic epoxy compound, butadiene (co)polymer epoxide, isoprene (co)polymer epoxide, (meth) acrylate (co)polymer, different Triglycidyl cyanurate and the like.

Specific examples of the oxetane compound in the curing agent may include carbonate dioxetane, xylene dioxetane, adipic acid dioxetane, and dioxyethylene terephthalate. Butane, cyclohexanedicarboxylic acid dioxetane, and the like.

The curing agent may be used in combination with the auxiliary curing compound such that the epoxy group of the epoxy compound or the oxetane backbone of the oxetane compound can undergo ring-opening polymerization. Examples of the auxiliary curing compound may include a polycarboxylic acid, a polycarboxylic acid anhydride, an acid generator, and the like. The polycarboxylic acid anhydrides may include those commercially available as epoxy resin curing agents. Specific examples of the epoxy resin curing agent may include commercially available products such as Adeka Hardener EH-700 (made by ADEKA Industry), Rikacid HH (made by New Japan Chemicals), MH -700 (manufactured by Nippon Chemical Co., Ltd.). These curing agents may be used singly or in combination of two or more thereof.

In order to further improve the film formability of the photosensitive resin composition, a surfactant may be used, and the surfactant preferably includes a siloxane surfactant or a fluorosurfactant.

Commercially available products of oxoxane surfactants may include DC3PA, DC7PA, SH11PA, SH21PA, and SH-8400 manufactured by Dow Corning Toray Silicones, and by General Electric Toshiba Aerobicane Corporation (TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, and TSF-4452 manufactured by GE Toshiba Silicones). Commercial products of the fluorine-based surfactant may include Megaface F554, F-470, F-471, F-475, F-482, F-489 (manufactured by Dainippon Ink Chemical Industry), BM -1000, BM-1100 (manufactured by BM Chemie), Flourad FC-135/FC-170C/FC-430 (manufactured by Sumitomo 3M Co., Ltd.), and the like. These surfactants may be used singly or in combination of two or more thereof.

The adhesion promoter is an additive for enhancing coatability and adhesion to a substrate, and may include reactivity having a group selected from the group consisting of a carboxyl group, a methacryl group, an isocyanate group, an epoxy group, and a mixture thereof. Substituted decane coupling agent. Specific examples of the decane coupling agent may include trimethoxy sulfonyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, and γ-isocyanate propyl three. Ethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

Specific examples of the antioxidant may include 2,2'-thiobis(4-methyl-6-tert-butylphenol) and 2,6-di-tert-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber may include 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Specific examples of the cohesion inhibitor may include sodium polyacrylate and the like.

The amount of the additive is from 0.01% by weight to 10% by weight, and preferably from 0.05% by weight to 2% by weight, based on the total weight of the solid content of the colored photosensitive resin composition.

For example, the colorant is added to the solvent, after which other components and additives can be added and stirred. Here, the colorant may be added in the form of a mill base in which the pigment is previously dissolved or dispersed in a solvent or an alkali-soluble resin. When the additive is in the form of a solution, it may be previously added to the solvent together with the coloring agent.

The colored photosensitive resin composition thus prepared is preferably used for the production of a display device, preferably a black matrix of a liquid crystal display device, or a column spacer or a black column spacer for maintaining a cell gap thereof.

In particular, the colored photosensitive resin composition of the present invention is preferably used for the manufacture of black column spacers (integrally formed black matrix integrated spacers), and the black column spacers are in which black matrix and The column spacers are not provided in a separately formed form, but are provided in a form in which a black matrix and a column spacer are integrally formed in a single pattern.

Further, the present invention is directed to a color filter comprising a black matrix, a pillar spacer or a black pillar spacer manufactured using the colored photosensitive resin composition.

Further, the present invention is directed to a display device including the color filter.

A typical patterning process for forming a black matrix, pillar spacer or black pillar spacer via photolithography may include: a) coating a colored photosensitive resin composition on a substrate; b) drying the solvent via prebaking; The exposed portion is cured by placing a photomask on the obtained film and irradiating the active light thereon; d) developing the process using an alkaline aqueous solution to dissolve the unexposed portion; and e) performing drying and post-baking.

The substrate is a glass substrate or a polymer substrate. The glass substrate preferably comprises soda lime glass, bismuth or bismuth containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borate glass or quartz. Moreover, the polymer substrate may comprise polycarbonate, acrylic, poly-p-phenylene Ethylene formate, polyether sulfide or polyfluorene.

In order to obtain a desired coating thickness, wet coating using a coating device such as a roll coater, a spin coater, a slit spin coater, a slit spin coater (or die coater), or an inkjet coater may be performed. Cloth process.

The prebaking process is carried out by heating using an oven, a hot plate or the like. Here, at the time of prebaking, the heating temperature and the heating time may be appropriately selected depending on the type of the solvent to be used, and may be, for example, a temperature of 80 ° C to 150 ° C and a time of 1 minute to 30 minutes.

After the prebaking process, the exposure process is performed via the reticle using the exposure machine, whereby only a portion corresponding to the pattern is sensitized. Here, examples of the irradiated light may include visible light, ultraviolet light, X-rays, and electromagnetic rays.

After the exposure process, alkaline development is performed to remove the unexposed portions of the colored photosensitive resin composition, thereby forming a desired pattern. The developer suitable for alkaline development may include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate. In particular, the developing process uses an alkaline aqueous solution containing 1% by weight to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate, at a temperature of 10 ° C to 50 ° C, and preferably 20 ° C to 40 ° C by means of The developing machine or the ultrasonic cleaning device is performed.

The post-baking process is performed by heat treatment under conditions of 80 ° C to 220 ° C and 10 minutes to 120 minutes to increase adhesion of the patterned film to the substrate. As with the prebaking process, the post-baking process is carried out using an oven, a hot plate, or the like.

The film thickness of the black matrix is preferably from 0.2 μm to 20 μm, more preferably from 0.5 μm to 10 μm, and still more preferably from 0.8 μm to 5 μm.

Moreover, the film thickness of the column spacer and the black column spacer is preferably from 0.1 μm to 8 μm, more preferably from 0.1 μm to 6 μm, and still more preferably from 0.1 μm to 4 μm.

A black matrix, column spacer or black column spacer manufactured using the colored photosensitive resin composition of the present invention may be excellent in properties such as optical density, adhesion, electrical insulating properties, and light blocking properties, and may also exhibit High heat resistance and solvent resistance improve the reliability of the liquid crystal display device.

A better understanding of the present invention can be obtained by the following examples, which are given by way of illustration and not by way of limitation. The examples of the invention may be appropriately changed and modified by those skilled in the art within the scope of the invention.

Preparation Example 1: Preparation of an alkali soluble resin

In a 1-liter flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was flowed at a rate of 0.02 liter/min to thereby form a nitrogen atmosphere, and 150 g of diethylene glycol methyl ethyl ether was added. Stir and heat to 70 °C. Subsequently, EDCPA, AA and (A) were added in respective proportions such that the total amount was 1 mol, dissolved in 150 g of diethylene glycol methyl ethyl ether, thereby obtaining a solution (for example, in the preparation example) In 1, 1 mol of EDCPA and 0.1 mol of AA were dissolved in 150 g of diethylene glycol methyl ethyl ether to obtain a solution, and in Preparation Example 2, 0.56 mol EDCPA, 0.2 mol AA, and 0.24 Mo The ear CYM-M100 is dissolved to obtain a solution). The prepared solution was added dropwise to the flask using a dropping funnel, and then 27.9 g (0.11 mol) 2,2'- as a photoinitiator dissolved in 200 g of diethylene glycol methyl ethyl ether. Azobis(2,4-dimethylvaleronitrile) was added dropwise to the flask over 4 hours using an additional dropping funnel. After the dropwise addition of the photoinitiator solution was terminated, the resulting solution was kept at 70 ° C for 4 hours, and then cooled to room temperature, thereby obtaining a copolymer solution.

EDCPA: (containing 3,4-epoxytricyclo[5.2.1.0,2,6]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2] mixed with 50:50 molar ratio .1.0,2,6]a mixture of decane-8-yl acrylate)

AA: Acrylic

CYM-M100: 3,4-epoxycyclohexylmethyl methacrylate

HEMA: hydroxyethyl methacrylate

4-META: 4-methylpropenyloxyethyl trimellitic anhydride

CHMA: cyclohexyl methacrylate

BzMA: benzyl methacrylate

Preparation Example 2: Preparation of a coloring dispersion solution

(1) Preparation of colored dispersion solution 1

A coloring dispersion solution was prepared using the composition of Table 2 below. As the dispersion resin, the alkali-soluble resins B1 to B6 of Preparation Example 1 were used, and a polymer dispersant (Disper BYK-2000) was used. PGMEA (propylene glycol monomethyl ether acetate) solvent was used. The mixture was dispersed for 8 hours at room temperature using a paint shaker. Dispersion was carried out using 0.1 mm zirconia beads. After the dispersion is completed, filtration is performed.

(2) Preparation of colored dispersion solution 2

A coloring dispersion solution was prepared in the same manner as above except that B2 was used as the dispersion resin in Table 2 instead of B1.

(3) Preparation of colored dispersion solution 3

A coloring dispersion solution was prepared in the same manner as above except that B3 was used as the dispersion resin in Table 2 instead of B1.

(4) Preparation of colored dispersion solution 4

A coloring dispersion solution was prepared in the same manner as above except that B4 was used as the dispersion resin in Table 2 instead of B1.

(5) Preparation of coloring dispersion solution 5

A coloring dispersion solution was prepared in the same manner as above except that B5 was used as the dispersion resin in Table 2 instead of B1.

(6) Preparation of coloring dispersion solution 6

A coloring dispersion solution was prepared in the same manner as above except that B6 was used as the dispersion resin in Table 2 instead of B1.

Examples 1 to 12 and Comparative Examples 1 to 9: Preparation of a colored photosensitive resin composition

A colored photosensitive resin composition was prepared by mixing the colored dispersion solution of Table 2 with an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The amount thereof is shown in the following Table 3, in which the solid content of the colored photosensitive resin composition was 20% by weight.

In Table 3, Example 1 and Example 5 used the colored dispersion solution of Preparation Example 2. (1). Example 2 and Example 6 The colored dispersion solution of Preparation Example 2. (2) was used. Example 3 and Example 7 The coloring dispersion solution of Preparation Example 2. (3) was used, and Example 4 and Example 8 to Example 12 were used for the color dispersion solution of Preparation Example 2. (4). Comparative Example 1 to Comparative Example 7 used the colored dispersion solution of Preparation Example 2. (4), Comparative Example 8 used the colored dispersion solution of Preparation Example 2. (5), and Comparative Example 9 used the coloration of Preparation Example 2. (6). Disperse the solution.

OBP: Organic Black Pigment (100CF, manufactured by BASF Corporation)

V29: C.I. Pigment Violet 29

B60: C.I. Pigment Blue 60

CB: carbon black

PI-R: red pigment (R194, CLARIANT)

PI-G: Green pigment (G58, DIC company)

Alkali soluble resin

B1 to B6: alkali-soluble resin of Preparation Example 1

Photopolymerizable compound: dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku Co., Ltd.)

Photoinitiator: 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone-1-(O-acetamidine) (Irgacure) OXE-02: Ciba (Ciba)

Dispersant: DisperBYK-2000

Additive 1: TAG-2713 (manufactured by K-PURE Co., Ltd.)

Additive 2: F554 (made by DIC)

Solvent: propylene glycol monomethyl ether acetate

Test Example 1. Measuring the properties of the colored photosensitive resin composition

1-1. Measuring optical properties

A glass substrate (manufactured by Corning Co., Ltd.) of 5 cm × 5 cm size was washed with a neutral detergent and water, and then dried. The colored photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 9 were applied onto a glass substrate by spin coating to have a final film thickness of 3.0 μm, and prebaked at 80 ° C to 120 ° C. Bake and then dry for 1 minute to 2 minutes to remove the solvent.

Thereafter, the exposure process is performed at an exposure amount of 25 mJ/cm ² (mJ/cm ² ) to 35 mJ/cm ² , and then post-baking is performed at 200 ° C to 250 ° C for 10 minutes to 30 minutes, thereby A colored substrate was produced, which was coated with a colored photosensitive resin composition on the front side without any pattern.

The optical properties of the colored substrate were measured using an ultraviolet-visible spectrophotometer (UV-2550, manufactured by Shimadzu Corporation), and in the wavelength range of 400 nm to 600 nm (indicating optical density) when evaluating optical properties And the measurement values at various wavelengths are measured in the range of 700 nm to 750 nm and 950 nm (corresponding to near-infrared light).

The evaluation criteria are as follows, and the results are shown in Table 4 below.

<Evaluation criteria>

400 nm to 600 nm

◎: 0.1T% or less (excellent)

○: more than 0.1T% to 0.2T% (good)

Δ: greater than 0.2T% to 0.3T% (general)

X: greater than 0.3T% (poor)

700 nm to 750 nm

◎: 8T% or less (excellent)

○: more than 8T% to 10T% (good)

Δ: greater than 10T% to 12T% (general)

X: 12T% or more (poor)

950 nm

◎: 17T% or more (excellent)

○: 15T% to less than 17T% (good)

Δ: 13T% to less than 15T% (general)

X: less than 13T% (poor)

1-2. Measurement reliability

The substrate was fabricated in the same manner as the method of manufacturing a substrate in the above optical quality measurement.

The substrate was cut into a size of 3 cm × 3 cm, immersed in NMP solvent, and then heated at 100 ° C for 60 minutes. Thereafter, the NMP solvent was separated and extracted, and the absorbance indicating the degree of bleeding in the NMP solvent was measured at 300 nm to 800 nm using an ultraviolet-visible spectrophotometer to evaluate the solvent resistance.

The evaluation criteria are as follows, and the results are shown in Table 4 below.

<Evaluation criteria>

○: 0.5 or less (good),

Δ: greater than 0.5 to 0.8 (general),

X: greater than 0.8 (poor)

1-3. Measuring elastic recovery rate

A glass substrate coated with a cured film was produced in the same manner as the method of the above 1-1 except that the pillar spacer pattern was formed. The pattern thickness and height of the manufactured substrate were measured in a reference state using SNU (SIS-2000, manufactured by SNU Corporation). Thereafter, a pressure was applied using a nano indenter (HM500, manufactured by Fisher) until the pattern was deformed by 1 μm. Here, a flat indenter was used as a nanoindenter to press at a rate of 2 millinewtons per second (mN/sec). After holding for 5 seconds at a 1 micrometer deformation position, the thickness and line width of the pattern were measured using SNU (SIS-2000, manufactured by SNU), and the elastic recovery rate was measured based on the change in pattern thickness before and after the test (indicating the deformation after deformation) The thickness of the pattern and the width of the line relative to the thickness of the pattern before the deformation and the line width).

<Evaluation rate of elastic recovery rate>

○: Good, 97% or more

Δ: generally, 95% to less than 97%

X: poor, less than 95%

The colored photosensitive resin compositions according to Examples 1 to 12 of the present invention are excellent in optical properties, reliability, and elastic recovery rate. In particular, further including carbon black Examples 5 to 8, Example 11 and Example 12 exhibited excellent optical properties in the range of 400 nm to 600 nm.

The color-sensitive photosensitive resin composition of Comparative Example 1 to Comparative Example 5 lacks at least one of an organic black pigment, a violet pigment, and a blue pigment, and its reliability and elastic recovery rate are very poor, and is from 700 nm to 750 nm. Or optical properties in the range of 950 nm.

The color-sensitive photosensitive resin compositions of Comparative Example 6 and Comparative Example 7 lack at least one of an organic black pigment, a violet pigment, and a blue pigment and contain other coloring pigments, and exhibit optical properties, reliability, and elastic recovery ratio. The colored photosensitive resin compositions of Comparative Example 8 and Comparative Example 9 in which the compound of Chemical Formula 1 or Chemical Formula 2 was not used as the alkali-soluble resin exhibited excellent optical properties, but the reliability and the elastic recovery rate were inferior.

Claims (14)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the colorant comprises an organic black pigment, a blue pigment, and a violet pigment, and The alkali-soluble resin contains a copolymer of the following Chemical Formula 1 or Chemical Formula 2: Wherein (A) is 3,4-epoxycyclohexylmethyl (meth)acrylate, 4-methylpropenyloxyethyl trimellitic anhydride or hydroxyethyl methacrylate, and in Chemical Formula 1, monomer a and single The molar ratio of the body b is 2:8 to 9:1, and in the chemical formula 2, the molar ratio of the monomer a, the monomer b to the monomer c is 2:3:5 to 8:1:1. The colored photosensitive resin composition according to claim 1, wherein the organic black pigment comprises at least one selected from the group consisting of indoleamine black, aniline black, and phthalocyanine. The colored photosensitive resin composition according to claim 1, wherein the purple pigment comprises a color selected from the group consisting of C.I. At least one of the group consisting of Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 31, and C.I. Pigment Violet 37. The colored photosensitive resin composition according to claim 1, wherein the blue pigment does not contain a center metal. The colored photosensitive resin composition according to claim 4, wherein the blue pigment comprises at least one selected from the group consisting of C.I. Pigment Blue 16, C.I. Pigment Blue 60, C.I. Pigment Blue 63, and C.I. Pigment Blue 66. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 3,000 to 20,000. The colored photosensitive resin composition according to claim 1, wherein the coloring agent is contained in an amount of from 13% by weight to 60% by weight, based on the total weight of the solid content of the colored photosensitive resin composition, and from 5% by weight to 60% by weight. % of the alkali-soluble resin, 5% by weight to 50% by weight of the photopolymerizable compound, and 0.1% by weight to 40% by weight of the photoinitiator, and based on the total weight of the colored photosensitive resin composition, 60 to 90% by weight of the solvent. The colored photosensitive resin composition according to claim 1, wherein the organic black pigment, the violet pigment, and the blue pigment in the colorant are mixed in a weight ratio of 1:0.08 to 2.5:0.2 to 3.3. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin and the photopolymerizable compound are mixed in a weight ratio of 1:1 to 5:1. The colored photosensitive resin composition of claim 1, wherein the coloring agent further comprises carbon black. The colored photosensitive resin composition according to claim 10, wherein the organic black pigment, the purple pigment, the blue pigment, and the carbon black in the coloring agent are 1:0.08 to 2.5:0.2 to 3.3:0.12 Mix to a weight ratio of 1.7. The colored photosensitive resin composition according to claim 1, further comprising at least one additive selected from the group consisting of a thermal initiator, a curing agent, a surfactant, a tackifier, an antioxidant, an ultraviolet absorber, and the like. Poly inhibitor. A color filter comprising a column spacer, a black matrix or a black column spacer manufactured using the colored photosensitive resin composition according to any one of claims 1 to 12. A display device comprising the color filter of claim 13.