KR101886992B1 - A photo sensitive resin composition, a color filter comprising a black metrics, a column spacer or black column spacer prepared by using the composition, and a display devide comprising the color filter - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition comprising a colorant containing an organic black pigment, a violet pigment and a blue pigment, a binder resin, a photopolymerizable compound containing 7 to 12 functional groups, a photopolymerization initiator and a solvent, A color filter including a matrix, a column spacer or a black column spacer, and a display device including the color filter.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter including a black matrix, a column spacer or a black column spacer manufactured using the same, and a display device including the color filter COLUMN SPACER OR BLACK COLUMN SPACER PREPARED BY USING THE COMPOSITION, AND A DISPLAY DEVIDE COMPRISING THE COLOR FILTER}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a black matrix prepared using the same, a color filter including a column spacer or a black column spacer, and a display device including the color filter, and more particularly to an organic black pigment, And a coloring agent comprising a blue pigment, a binder resin, a photopolymerizable compound containing 7 to 12 functional groups, a photopolymerization initiator and a solvent, a black matrix, a column spacer or a black column spacer prepared using the same, And a display device including the color filter.

A color filter can be embedded in a color photographing apparatus of an image sensor such as a complementary metal oxide semiconductor (CMOS), a charge coupled device (CCD), or the like and used to actually obtain a color image. In addition, the color filter is widely used for a photographing element, a plasma display panel (PDP), a liquid crystal display (LCD), a field emission display (FEL), a light emitting display (LED) and the like. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.

The color filter is prepared by uniformly applying a colored photosensitive resin composition containing a coloring agent corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed by spin coating and then heating and drying (hereinafter, (Hereinafter sometimes referred to as "post-baking") is repeated for each color to form pixels of each color, if necessary, by exposing and developing the resulting coating film . In recent years, a large-sized display has progressed at a high speed and a high contrast ratio is continuously required. Therefore, a method of using a dye instead of the pigment dispersion method, which was conventionally used as a coloring method of a colored photosensitive resin composition, or using a dye and a pigment simultaneously . However, a colored photosensitive resin composition for a color filter using a dye and a colored photosensitive resin composition for a hybrid type color filter using both a dye and a pigment simultaneously can provide a color filter excellent in transmittance. However, The sensitivity may be lowered depending on the kind of the ink. Therefore, studies have been actively made to solve the above problems and to prevent the sensitivity of the color filter from deteriorating.

On the other hand, Korean Patent Registration No. 10-0529638 discloses a photopolymerizable resin composition containing an N-phenylglycine and a triazine-based compound excellent in adhesion, resolution, surface margin and internal curability as an initiator, It seems to be insufficient for improving the sensitivity of the filter pattern formation.

Korean Patent No. 10-0529638

An object of the present invention is to provide a colored photosensitive resin composition which is easy to form a pattern, has excellent processability, and is excellent in optical density and reliability.

It is another object of the present invention to provide a color filter comprising a black matrix, a column spacer or a black column spacer made of a colored photosensitive resin composition.

In order to achieve the above object,

The present invention relates to a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the colorant comprises an organic black pigment, a violet pigment and a blue pigment,

Wherein the photopolymerizable compound is a compound containing 7 to 12 functional groups.

The present invention also provides a color filter comprising a black matrix, a column spacer or a black column spacer made of the colored photosensitive resin composition of the present invention.

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

The colored photosensitive resin composition of the present invention is excellent in processability due to easy pattern formation, and has an excellent optical density and reliability.

Further, the color filter and the display device made of the colored photosensitive resin composition of the present invention have an excellent color reproduction effect.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

Wherein the colorant comprises an organic black pigment, a violet pigment and a blue pigment,

Wherein the photopolymerizable compound is a compound containing 7 to 12 functional groups.

The present invention includes a compound containing an organic black pigment, a violet pigment and a blue pigment as a colorant and a compound containing 7 to 12 functional groups as a photopolymerizable compound, thereby enabling fine control of photoreactivity and facilitating formation of a step and a pattern Thereby providing a colored photosensitive resin composition having excellent processability, reliability, and optical density.

Hereinafter, the colored photosensitive resin composition of the present invention will be described in detail for each component.

(A) Colorant

The colorant used in the present invention is one which is shielding against visible light, and the colorant of the present invention includes an organic black pigment, a violet pigment and a blue pigment.

The organic black pigment may include at least one selected from the group consisting of lactam black, aniline black and perylene black, and more specifically, 100 CF (Basf). By including the organic black pigment, the optical density can be improved, the infrared region can be not affected, and the dielectric constant and the transmittance can be improved.

The violet pigment serves to improve the optical density (O.D.) by reducing the transmittance in the region of 400 to 600 nm. By using the violet pigment as a colorant, the content of the organic black can be reduced, and the reliability of the colored photosensitive resin composition can be further improved. The type of the violet pigment is not particularly limited, but C.I. Pigment Violet 19, 23, 29, 31 and 37, and it is preferable to use at least one selected from the group consisting of C.I. It is most preferred to use Pigment Violet 29.

The blue pigment is a compound that does not include a center metal. When the center metal is present, it may affect the liquid crystal driving. In the present invention, by using a compound that does not include a center metal as a blue pigment, . In the present invention, the type of the blue pigment is not particularly limited as long as it is a compound that does not include a center metal. Pigment Blue 16, 60, 63 and 66 is preferably used, and C.I. Pigment Blue 60 is most preferably used.

In the present invention, the colorant is contained in an amount of 15 to 50% by weight, preferably 25 to 45% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is included in an amount of from 13 to 50% by weight, the optical density is excellent, and the pattern formation and step formation are easy, and the processability is excellent.

More specifically, the colorant is a mixture of an organic black pigment, a violet pigment and a blue pigment in a weight ratio of 1: 0.1 to 1.7: 0.25 to 3.3, preferably 1: 0.2 to 1.4: 0.5 to 2.9 will be.

When the organic black pigment is contained in the above weight ratio, a colored photosensitive resin composition excellent in optical density and reliability can be obtained. The organic black pigment may be contained in an amount of 6 to 20% by weight, and preferably 8 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 excellent in optical density and reliability can be obtained. In addition, the violet pigment may be contained in an amount of 2 to 10% by weight, preferably 4 to 10% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

When the blue pigment is contained in the above weight ratio, a colored photosensitive resin composition having an excellent optical density can be obtained. The blue pigment may be contained in an amount of 5 to 20% by weight, and preferably 10 to 20% by weight based on the total weight of the solid content of the colored photosensitive resin composition.

In addition, the colorant of the present invention may further include carbon black. When the colorant further contains carbon black, the colorant may be mixed in a weight ratio of 1: 0.1 to 1.7: 0.25 to 3.3: 0.15 to 1.7 in terms of the weight ratio of the organic black pigment, the violet pigment, the blue pigment and the carbon black. Further, it may preferably be mixed at a weight ratio of 1: 0.2 to 1.4: 0.5 to 2.9: 0.2 to 1. The carbon black may be contained in an amount of 3 to 10% by weight, and preferably 4 to 7% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the carbon black is contained in the above weight ratio, a colored photosensitive resin composition having an excellent optical density can be obtained.

In the present invention, the solid content in the colored photosensitive resin composition means the sum of the components from which the solvent has been removed.

In addition, it is preferable to use a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a1) by containing the pigment dispersant (a1), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in the solution have.

(a1) pigment dispersant

The pigment dispersant is added for deaggregation of the pigment and maintenance of stability. Specific examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, a positive surfactant, a polyester surfactant, and a polyamine surfactant. , Which may be used alone or in combination of two or more.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate, And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

In addition, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines have.

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and the like may be used as the acrylate-based dispersing agent, The rate-based dispersing agents may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) Amine salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free ) Oil-based dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide; And phosphate esters.

DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, and DISPER BYK-160 available from BYK (Big) Chemie are examples of commercially available pigment dispersants of other resin types. BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

In addition to the acrylate-based dispersant, other resin-type pigment dispersants may be used alone or in combination of two or more, and may be used in combination with an acrylate-based dispersant.

The pigment dispersant is contained in an amount of more than 0 to 1 part by weight, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the colorant. When the pigment dispersant is contained in an amount exceeding 0 to 1 part by weight, the uniformly dispersed pigment can be obtained.

(B) binder resin

The binder resin usually makes the unexposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition alkali-soluble, and also acts as a binder resin and a dispersing medium for the coloring agent.

The binder resin may be any polymer as long as it is soluble in the alkaline developer used in the development step for the production of the color filter. However, in the present invention, it is preferable to use a binder resin containing an epoxy group. The use of a binder resin containing the epoxy group can improve the reliability of the colored photosensitive resin composition.

The binder resin includes, for example, a copolymer of a monomer containing an epoxy group and another monomer copolymerizable with the monomer.

Specific examples of the monomer containing an epoxy group include 3,4-epoxytricyclo [5.2.1.0,2,6] decan-9-yl acrylate, 3,4-epoxytricyclo [5.2.1.0, 2,6] decan-8-yl acrylate, and the like.

Specific examples of the other monomer copolymerizable with the monomer containing an epoxy group include unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, Vinyl monomers, vinyl monomers, vinyl compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes and polysiloxanes having monoacyloyl groups or monomethacryloyl groups at the ends of the polymer molecular chain, Two or more species may be used in combination.

The weight average molecular weight of the binder resin is 3,000 to 20,000, preferably 5,000 to 15,000.

Also, the acid value of the binder resin is 50 to 200 mgKOH / g on the basis of the solid content, and the developability against the alkali development within the above range is excellent, the occurrence of the residue can be suppressed and the adhesion of the pattern can be improved.

The binder resin is included in the colored photosensitive resin composition in an amount of 5 to 85% by weight, preferably 5 to 70% by weight based on the total weight of the solid components. When the content of the binder resin is within the above-mentioned range, pattern formation is easy and resolution and residual film ratio are improved.

(C) Photopolymerization  compound

The photopolymerizable compound contains an unsaturated bond and forms a colored photosensitive resin layer by proceeding a photoreaction with the photopolymerization initiator, and should be a compound capable of polymerizing under the action of a photopolymerization initiator (D) described later.

In the present invention, the photopolymerizable compound uses a compound containing 7 to 12 functional groups, preferably a compound containing 8 to 10 functional groups, and the functional group is a (meth) Acrylate group.

The photopolymerizable compound containing 7 to 12 functional groups specifically includes, for example, tripentaerythritol hexa (meth) acrylate, tetrapentaerythritol hexa (metha) acrylate, polypentaerythritol polyacrylate, and urethane Acrylate. Preferably, the compound of the following formula (1), which is an 8-functional photopolymerizable compound, or the compound of the following formula (2), which is a 10-function photopolymerizable compound may be used.

[Chemical Formula 1]

(2)

The photopolymerizable compound is included in the colored photosensitive resin composition of the present invention in an amount of 5 to 50% by weight, preferably 7 to 45% by weight based on the total weight of the solid component. The photopolymerizable compound can improve the strength and flatness of the pixel portion in the range of 5 to 50% by weight.

In addition, the binder resin of the present invention and the photopolymerizable compound are mixed at a weight ratio of 1: 1 to 5: 1, preferably at a weight ratio of 1.2: 1 to 3.7: 1. When the binder resin and the photopolymerizable compound are mixed in a weight ratio of 1: 1 to 5: 1, the processability is improved and a colored photosensitive resin composition that can easily form a pattern can be provided.

(D) Light curing Initiator

The photopolymerization initiator can be used without limitation as long as it can polymerize the photopolymerizable compound. Preferably, the photopolymerization initiator is an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, Based compound, a triazine-based compound, a non-imidazole-based compound, an oxime-based compound, and a thioxanthone-based compound.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (2-hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan- ] Propane-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoisobutyl ether.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ' -Tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Ethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4 dimethoxyphenyl) ethenyl] -1 , 3,5-triazine, and the like.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- ) Diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group .

More preferably, it is selected from the group consisting of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl- And the like.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available oxime compounds may be OXE01 and OXE02 of BASF.

The thioxanthone compound is specifically exemplified by 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Santon et al.

These photopolymerization initiators may be used singly or in combination of two or more.

In the present invention, the photopolymerization initiator is contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the total solid content of the colored photosensitive resin composition.

The colored photosensitive resin composition becomes highly sensitive within the range of 0.1 to 40% by weight, and the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness on the surface of the pixel portion can be improved.

In the present invention, a photopolymerization initiator may be used in addition to the photopolymerization initiator.

The photopolymerization initiation assistant is a compound used for promoting polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiation assistant include an amine compound or an alkoxyanthracene compound.

Specific examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid 2 N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzphenone (collectively, Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable.

Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl- Diethoxyanthracene and the like.

Commercially available photopolymerization initiators may also be used. Commercially available photopolymerization initiators include trade names " EAB-F " (manufactured by Hodogaya Chemical Industry Co., Ltd.).

 When the photopolymerization initiator is used, it is preferably used in an amount of usually 0 to 10 mol, preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator. When the photopolymerization initiator is used in the range of more than 0 to 10 moles, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the colored photosensitive resin composition can be improved.

(E) Solvent

The solvent used in the conventional colored photosensitive resin composition can be used without particular limitation so long as it is effective to dissolve the other components contained in the colored photosensitive resin composition. In particular, the solvent may be selected from ethers, acetates, aromatic hydrocarbons, ketones, Alcohols or esters are preferred.

Examples of the ethers 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 ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 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 acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

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

The ketones include, for example, methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

The alcohols include, for example, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and 4-hydroxy-4-methyl-2-pentanone.

Examples of the esters include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and? -Butyrolactone.

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

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

The solvent is contained in an amount of 60 to 90% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the range of 60 to 90% by weight, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

(F) Additive

The colored photosensitive resin composition of the present invention includes other additives according to the needs of those skilled in the art, as long as the objects of the present invention are not impaired, in addition to the above-mentioned components.

The additive may specifically include, for example, at least one additive selected from the group consisting of another polymer compound, a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- In the invention, it is preferable to include a thermal initiator as an additive.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin; And thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester and polyurethane.

The thermal initiator causes a curing reaction by heat to maximize the initiation efficiency. The thermal initiator may be a peroxide-based compound.

Specific examples of the thermal initiator include, but are not limited to, tetramethyl butyl peroxyneodecanoate (eg Perocta ND, NOF), bis (4-butylcyclohexyl) peroxydicarbonate (eg Peroyl TCP Perfluoroalkane (ex. Perbutyl ND, manufactured by NOF), dipropyl peroxydicarbonate (ex. Peroyl NPP, manufactured by NOF Corporation), di (2-ethylhexyl) peroxycarbonate, butyl peroxyneodecanoate , NOF Corp.), diisopropyl peroxy dicarbonate (e.g., Peroyl IPP, NOF), diethoxyethyl peroxydicarbonate (e.g., Peroyl EEP, NOF), diethoxy (Peroyl OEP, NOF), hexyl peroxydicarbonate (e.g., Perhexyl ND, NOF), dimethoxybutyl peroxydicarbonate (e.g. Peroyl MBP, NOF Peroyl SOP, NOF), dibutyl peroxydicarbonate, dicetyl peroxy dicyclohexylcarbodiimide, bis (3-methoxy-3-methoxybutyl) peroxydicarbonate Dicabo Peroxypivalate, hexyl peroxypivalate (ex. Perhexyl PV, NOF), and the like. Perbutyl (NOF), trimethyl hexanoyl peroxide (e.g., Peroyl 355, NOF), dimethylhydroxybutyl peroxyneodecanoate (ex Luperox 610M75) , Atofina (manufactured by Atofina), amyl peroxyneodecanoate (ex Luperox 546M75, Atofina), butyl peroxyneodecanoate (ex Luperox 10M75, Atofina), t-butyl peroxy (Luperox 546M75, Alofina), t-butyl peroxypivalate, t-amylperoxy-2-ethylhexanoate, lauryl peroxide , Dilauroyl peroxide, didecanoyl peroxide, benzoyl peroxide, dibenzoyl peroxide, 2,2-bis (tert-butylperoxy) butane, 1,1- Butyl peroxy) -2,5-dimethylhexane, 2,5-bis (tert-butylperoxy) -1-methylethyl) benzene, 1,1- Butyl peroxy) -3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, Peracetic acid, and potassium persulfate, which may be used alone or in combination with one or more of the following: ). ≪ / RTI >

With respect to the content of the thermal initiator, it is preferably contained in an amount of 1 to 10% by weight, and more preferably 1 to 5% by weight based on the total solid content of the colored photosensitive resin composition. When it is contained in the above-mentioned contents, it is more preferable for fairness and undercut.

The curing agent is used for increasing the curing depth and mechanical strength, and specific examples thereof 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 include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing assistant compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agents include commercial products such as ADEKA HARDONA EH-700 (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (manufactured by New Japan Chemical Co., Ltd.) Manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film-forming property of the photosensitive resin composition, and a silicone surfactant or a fluorine surfactant may be preferably used.

TS-4440, TSF-4300, TSF-4445, TSF-4446, and TSF-4400 of GE Toshiba Silicones such as DC3PA, DC7PA, SH11PA, SH21PA and SH-8400 from Dow Corning Toray Silicone Co., 4460 and TSF-4452. F-472, F-482 and F-489 (Dainippon Ink and Chemicals, Inc.), BM-1000 and BM-1100 (trade names, (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M Co., Ltd.), and the like. The above-exemplified surfactants may be used alone or in combination of two or more.

The adhesion promoter is an additive which is used for improving coatability and adhesion to a substrate, and is a silane coupling agent containing a reactive substituent selected from the group consisting of a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, . Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, r- Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

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

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

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

For example, a coloring agent may be added to a solvent, followed by addition of the rest of the composition and other additives, followed by stirring. The colorant may be added in the form of a mill base in which a pigment or the like is dissolved or dispersed in advance in a solvent or a binder resin. The additive, if in solution form, may be added in advance to the solvent along with the colorant.

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

In particular, the colored photosensitive resin composition of the present invention can be suitably used for producing a black column spacer (black matrix integrated spacer), and the black column spacer does not form a black matrix and a column spacer, Means that the matrix and the column spacer are integrally formed.

The present invention also relates to 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 relates to a display device including the color filter

A typical patterning process for forming a black matrix, column spacer or black column spacer according to the photolithography method

a) applying a colored photosensitive resin composition to a substrate;

b) prebaking step of drying the solvent;

c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking.

A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.

The coating may be performed by a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after exposure is performed for the purpose of removing the colored photosensitive resin composition in a portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As the developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .

The post-baking is performed in order to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking is performed by using an oven, a hot plate, or the like as in pre-baking.

In this case, the thickness of the black matrix is preferably 0.2 to 20 占 퐉, more preferably 0.5 to 10 占 퐉, and particularly preferably 0.8 to 5 占 퐉.

The film thickness of the column spacer and the black column spacer is preferably 0.1 탆 to 8 탆, more preferably 0.1 탆 to 6 탆, and particularly preferably 0.1 탆 to 4 탆.

The black matrix, the column spacer or the black column spacer made of the colored photosensitive resin composition of the present invention is excellent in physical properties such as optical density, adhesion, electrical insulation and light shielding property, and is excellent in heat resistance and solvent resistance, It is possible to improve the reliability.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Manufacturing example  1. Preparation of binder resin

277 g of methoxybutyl acetate was added to an internal 1-L separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the mixture was heated to 80 DEG C and 3,4-epoxytricyclo [5.2.1.0 , 2,6] decan-9-yl acrylate and 3,4-epoxytricyclo [5.2.1.0,2,6] decan-8-yl acrylate in a molar ratio of 50:50, 49 g of the acid and 23 g of azobisdimethylvaleronitrile in 350 g of methoxybutyl acetate was added dropwise over 5 hours. Thereafter, the reaction was continued for 3 hours to prepare a binder resin solution.

Example  1 to 11 and Comparative Example  1 to 9. Preparation of colored photosensitive resin composition

A mixture of a colorant, a binder resin, a dispersant and a solvent was dispersed in a paint shaker at room temperature for 8 hours. Dispersion was carried out using 0.1 mm zirconia beads, followed by dispersion and filtration to prepare a colored dispersion.

A colored photosensitive resin composition was prepared by mixing the above colored dispersion with a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and the content thereof is shown in Table 1 below.

[Table 1]

(Unit: g)

OBP: Organic Black Pigment (100CF, BASF)

V29: C.I. Pigment Violet 29

B60: C.I. Pigment Blue 60

CB: carbon black

Red: C.I. Pigment Red 264

Binder: The binder resin prepared in Production Example 1

Photopolymerizable compound (using a (meth) acrylate group as a functional group)

M1: Viscoat # 802-1 (Seven functionalities, Osaka Organic Chemical)

M2: Viscoat # 802 (octahedral, Osaka Organic Chemical)

M3: Viscoat # 802-2 (10-functional, Osaka Organic Chemistry)

M4: DIPENTAERYTHRITOL HEXAACRYLATE (DPHA) (6-functional, Shin Nakamura)

M5: Dendritic Polyester Poly acrylate (15-function, Osaka Yuki Chemical)

Photopolymerization initiator (PI): 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone- 1- (O- acetyloxime) (Irgacure OXE- four)

Additive (D1): Solpus 5000 (manufactured by Lubrisol)

Additive (D2): F554 (DIC)

Solvent: Propylene glycol monomethyl ether acetate

Experimental Example  1. Measurement of physical properties of colored photosensitive resin composition

1-1. Board Fabrication

A 5 cm x 5 cm glass substrate (Corning) was cleaned with a neutral detergent and water and dried. Each of the colored photosensitive resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 9 was spin-coated on the glass substrate to a final film thickness of 3.0 (+/- 0.2) 占 퐉 and prebaked at 80 to 120 占 폚 Followed by drying for 1 to 2 minutes to remove the solvent to form a pre-cured film.

Thereafter, a pattern was formed through exposure with an exposure amount of 25 to 35 mJ / cm ² through a photomask, and an unexposed area was removed using an aqueous alkali solution. Followed by baking at 200 to 250 DEG C for 10 to 30 minutes to prepare a colored substrate.

1-2. Pattern characteristics

A pre-cured film having a thickness of 3.0 (+/- 0.2) 占 퐉 was formed in accordance with the above-mentioned cured film production method, and then exposed with a photomask and developed and exposed under the same conditions as in the development of the cured film. The pattern line width (pattern: 50 mu m) of the formed cured film was measured to evaluate the pattern characteristics. The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Evaluation Criteria>

◎: Less than ± 20 (very good)

?: More than ± 20 and less than or equal to 25 (excellent),

?: More than ± 25 and less than 30 (good)

X: Over ± 30 (insufficient)

1-3. Reliability measurement

A substrate was prepared in the same manner as in the production of the substrate prepared in the measurement of the pattern characteristics, except that a patterned photosensitive resin composition without the use of a photomask was coated on the entire surface.

The substrate was cut into a size of 3 x 3 cm, immersed in NMP solvent, and then heated at 100 DEG C for 60 minutes. After that, only the NMP solvent was extracted, and the degree of dissolution in NMP solvent was measured by UV-vis spectrometer at 300 to 800 nm to confirm the solvent resistance.

The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Evaluation Criteria>

⊚: not more than 0.3 (very good)

?: Not less than 0.3 but not more than 0.5 (excellent),

?: Not less than 0.5 but not more than 0.8 (insufficient)

X: greater than 0.8 (worse)

1-4. Optical density  Measure

A substrate was prepared in the same manner as in the production of the substrate prepared in the measurement of the pattern characteristics, except that a patterned photosensitive resin composition without the use of a photomask was coated on the entire surface.

The transmittance at 550 nm was measured using an optical density meter (361T, X-lite) to determine the optical density for a thickness of 1 mu m. The evaluation criteria are as follows, and the results are shown in Table 2 below.

<Evaluation Criteria>

◎: ± 1.3 or more (very good)

?: Not less than 1.0 and not more than 1.3 (excellent),

?: 0.5 or more and less than 1.0 (good)

X: Less than ± 0.5 (insufficient)

[Table 2]

Examples 1 to 11, which are the colored photosensitive resin compositions of the present invention, showed excellent pattern characteristics, reliability, and optical density.

The colored photosensitive resin compositions of Comparative Examples 1 to 5, which did not contain at least one of the organic black pigment, the violet pigment and the blue pigment, showed poor reliability.

The colored photosensitive resin compositions of Comparative Examples 6 and 7, which contained no pigments of organic black pigment, violet pigment and blue pigment, and contained pigments of different colors, showed poor reliability and / or poor optical density , The colored photosensitive resin compositions of Comparative Examples 8 and 9 in which the functional group was out of the range of 7 to 12 with the photopolymerizable compound had a low pattern characteristic and a tendency that the reliability was deteriorated. Thus, when all of the constitution of the present invention is not included, It was confirmed that the desired effect can not be achieved.

Claims (15)

A colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
Wherein the colorant comprises an organic black pigment, a blue pigment and a violet pigment,
Wherein the photopolymerizable compound is a compound containing 7 to 12 functional groups and at least one compound selected from the group consisting of the following formulas (1) and (2):
[Chemical Formula 1]

(2)

The colored photosensitive resin composition according to claim 1, wherein the organic black pigment comprises at least one selected from the group consisting of lactam black, aniline black, and perylene black. 3. The composition of claim 1, wherein the violet pigment is selected from the group consisting of C.I. Pigment Violet 19, 23, 29, 31 and 37. The colored photosensitive resin composition according to claim 1, The colored photosensitive resin composition according to claim 1, wherein the blue pigment does not contain a center metal. The method of claim 4, wherein the blue pigment is selected from the group consisting of C.I. Pigment Blue 16, 60, 63 and 66. The colored photosensitive resin composition according to claim 1, The colored photosensitive resin composition according to claim 1, wherein the binder resin comprises an epoxy group. The colored photosensitive resin composition according to claim 1, wherein the photopolymerizable compound is a compound containing 8 to 10 functional groups. The photosensitive resin composition according to claim 1, which comprises 15 to 50% by weight of a colorant, 5 to 60% by weight of a binder resin, 5 to 50% by weight of a photopolymerizable compound and 0.1 to 40% by weight of a photopolymerization initiator based on the total weight of solid components in the colored photosensitive resin composition And 60 to 90% by weight of a solvent based on the total weight of the colored photosensitive resin composition. 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: 0.1 to 1.7: 0.25 to 3.3. The colored photosensitive resin composition according to claim 1, wherein the binder resin and the photopolymerizable compound are mixed in a weight ratio of 1: 1 to 5: 1. The colored photosensitive resin composition according to claim 1, wherein the colorant further comprises carbon black. 12. The colored photosensitive resin composition according to claim 11, wherein the organic black pigment, the violet pigment, the blue pigment and the carbon black in the colorant are mixed in a weight ratio of 1: 0.1 to 1.7: 0.25 to 3.3: 0.15 to 1.7. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises at least one additive selected from the group consisting of a thermal initiator, a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, Sensitive resin composition. A color filter comprising a column spacer, a black matrix, or a black column spacer made of the colored photosensitive resin composition according to any one of claims 1 to 13. A display device comprising the color filter of claim 14.