TW201510655A - Colored photosensitive resin composition, color filter, and liquid crystal display device having the same - Google Patents

Abstract

The present invention provides a colored photosensitive resin composition, comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F), the colorant (A) comprising one or more dyes, and the antioxidant (E) comprising a mixture of a phenol-based antioxidant and a sulfur-based antioxidant, a color filter formed by using the composition, and a liquid crystal display device having the color filter. The colored photosensitive resin composition according to the present invention has excellent heat-resistance and provides high luminance.

Description

Colored photosensitive resin composition, color filter, and liquid crystal display device having the same

The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same. In particular, the present invention provides a colored photosensitive resin composition which has excellent heat resistance whereby less discoloration and high brightness after a high temperature process; a color filter formed by using the composition; and having the filter A liquid crystal display device for color chips.

Color filters have been widely used in imaging devices and liquid crystal displays (LCDs), and their applications are expanding. Conventional color filters are prepared by uniformly coating a colored photosensitive resin composition containing a red, green or blue pigment on a black matrix substrate having a black pattern formed thereon, followed by heating and drying to obtain a resulting coating layer. The film is exposed and developed, and if necessary, further heated and hardened, thereby forming pixels of respective colors, and the above procedure is repeated for each color.

The colored photosensitive resin composition usually contains a pigment, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator. To form a black matrix, the photosensitive resin composition contains a black pigment.

Korean Patent Application Publication No. 2009-0066076 discloses a photosensitive resin composition for a color filter comprising an acrylic binder resin, an acrylic carboxylate resin containing a double bond, a photopolymerizable monomer, and photopolymerization Initiators, pigments, antioxidants and solvents. The composition uses, as an antioxidant, a mixture of a first antioxidant selected from the group consisting of a sterol-based compound, an amine-based compound, a phenol-based compound, and a mixture thereof, and a second antioxidant including a phosphite-based compound. Thereby, the photosensitive resin composition is prevented from being oxidized and its thermal stability is improved.

However, since a color filter prepared using a pigment-only photosensitive resin composition has low brightness, a photosensitive resin composition containing a dye has been studied to increase brightness. However, the dye-containing composition is difficult to obtain the desired brightness due to low heat resistance.

An object of the present invention is to provide a colored photosensitive resin composition which has excellent heat resistance whereby less discoloration and high brightness are provided after a high temperature process.

Another object of the present invention is to provide a color filter formed by using the colored photosensitive resin composition.

It is still another object of the present invention to provide a liquid crystal display device having the color filter.

According to an aspect of the present invention, there is provided a coloring photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an antioxidant. (E) and solvent (F), the colorant (A) comprises one or more dyes and the antioxidant (E) comprises a mixture of a phenol-based antioxidant and a sulfur-based antioxidant.

According to another aspect of the present invention, a color filter formed by using the colored photosensitive resin composition is provided.

According to still another aspect of the present invention, a liquid crystal display device having the color filter is provided.

The colored photosensitive resin composition of the present invention uses a phenol-based antioxidant and is based on A mixture of sulfur antioxidants acts as an antioxidant, and one or more dyes having low heat resistance as a colorant, thereby improving heat resistance and providing a color filter having high brightness.

[Best way]

The invention is described in more detail below.

One embodiment of the present invention relates to a coloring photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), and an antioxidant ( E) and solvent (F), the colorant (A) comprises one or more dyes and the antioxidant (E) comprises a mixture of a phenol-based antioxidant and a sulfur-based antioxidant.

Colorant (A)

In one embodiment of the invention, the colorant (A) is characterized by comprising one or more dyes, especially red dyes.

The dye may be any dye conventionally used in the art, such as a cyano-based dye, a dibenzopyran-based dye, an azo-based dye, a ruthenium-based dye, a metal-based complex-based dye, Quinoline-based dyes and pyrazolone-based dyes.

The colorant (A) may further comprise one or more pigments together with the dyes.

Pigments may include inorganic pigments such as metal oxides, metal complexes, and inorganic salts, including barium sulfate, and are classified as pigments in the Color Index (The Society of Dyers and Colourists). Organic pigments. Organic pigments are preferred in terms of heat resistance and color development.

For example, a compound classified as a pigment in the color index (British Dyers Institute) may be, but is not limited to, the following number of color index (C.I.) compounds.

CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214; CI Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 And 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264 and 265.

Among the above pigments, at least one selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Red 177, CI Pigment Red 242, and CI Pigment Red 254.

The above pigments may be used singly or in combination of two or more. For example, a mixture of C.I Pigment Red 254 and C.I. Pigment Red 177 can be preferably used to form red pixels.

The content of the colorant (A) is preferably from 5 to 70% by weight, more preferably from 10 to 50% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention.

The dye content is preferably from 0.5 to 100% by weight, more preferably from 1 to 60% by weight, based on the total solid content of the colorant (A). When the amount of the dye is in the range of 1 to 60% by weight, high brightness can be obtained, thereby allowing sufficient pattern formation and formation of a high-quality color filter pattern.

Adhesive resin (B)

In one embodiment of the present invention, the binder resin (B) may be a copolymer of a carboxyl group-containing monomer and other monomers copolymerizable with the monomers.

For example, other copolymerizable monomers may be monomers containing carbon-carbon unsaturated bonds, including aromatic vinyl compounds such as styrene, alpha-methyl styrene, vinyl toluene, etc.; unsaturated carboxylic acid esters Compounds such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid Benzyl methyl ester, benzyl methacrylate, etc.; An unsaturated carboxylic acid aminoalkyl ester compound such as aminoethyl acrylate or the like; an unsaturated carboxylic acid glycidyl ester compound such as glycidyl methacrylate or the like; a carboxylic acid vinyl ester compound such as vinyl acetate, Vinyl propionate or the like; vinyl cyanide compound such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, etc.; unsaturated oxetanecarboxylate compound such as 3-methyl-acryloxymethyl group Oxycyclobutane, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-B 3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-methyl-3-methylpropenyloxy Ethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-methyl-3-methylpropenyloxyethyloxetane, and the like.

The above monomers may be used singly or in combination of two or more.

The binder resin (B) may have a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 1.5 to 6.0, preferably 1.8 to 4.0. When the molecular weight distribution of the binder resin is in the range of 1.5 to 6.0, the developability can be improved.

The content of the binder resin (B) is preferably from 5 to 90% by weight, more preferably from 10 to 70% by weight, based on the total solid content of the colored photosensitive resin composition. When the amount of the binder resin (B) is in the range of 5 to 90% by weight, the solubility in the developing solution may be sufficient, whereby it is difficult to produce development residue on the substrate of the non-pixelized portion, and it is possible to prevent The film of the pixelated portion in the exposed region is lowered during development, thereby allowing the non-pixelated portion to leak well.

Photopolymerizable monomer (C)

In one embodiment of the present invention, the photopolymerizable monomer (C) is a monomer which can be polymerized by living radicals or acid generated by irradiation from a photopolymerization initiator.

Examples of the photopolymerizable monomer may include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol. Diacrylate, isovalerol acrylate, pentaerythritol diacrylate, isovalerol Acrylate, diisopentyl alcohol diacrylate, diisopentaerythritol triacrylate, diisopentaerythritol pentaacrylate, diisopentyl alcohol hexaacrylate, bisphenol A diacrylate, trimethylol Propane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like.

The photopolymerizable monomer (C) content is preferably from 5 to 45% by weight, more preferably from 10 to 35% by weight, based on the total solid content of the colored photosensitive resin composition. When the amount of the photopolymerizable monomer (C) is in the range of 5 to 45% by weight, the strength and smoothness of the pixel can be improved.

Photopolymerization initiator (D)

In one embodiment of the present invention, if the photopolymerization initiator (D) can be used to polymerize the binder resin (B) and the photopolymerizable monomer (C), it is not limited. In particular, the photopolymerization initiator may be selected from the group consisting of triazine, acetophenone, biimidazole compound, hydrazine compound, and mixtures thereof, depending on the polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like.

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-mallowyl-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 .

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-methyl thiophene Benzyl)-2-morpholinylpropan-1-one, 2-benzyl-2-ylaminoamino-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-morpholinylphenyl)butan-1-one.

Examples of the biimidazole-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-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole, 2,2-dual (2 ,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole and its phenyl group at the 4,4',5,5 position is substituted with an alkoxycarbonyl group Imidazole. Among them, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4 , 4',5,5'-tetraphenylbiimidazole and 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-linked Imidazole is preferred.

Examples of the oxime compound may include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, and compounds of the formulae (I) to (III):

In addition, other photopolymerization initiators known in the art can be used together unless they destroy the effects of the present invention. The other photopolymerization initiator may be, for example, a compound based on benzoin, benzophenone, thioxanthone or oxime, which may be used singly or in combination of two or more.

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

Examples of the benzophenone-based compound may include benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide. , 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the thioxanthone-based compound may include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthene. ketone.

Examples of the ruthenium-based compound may include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene.

Further, examples of other photopolymerization initiators may include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate and titanium titanate compound.

Further, the photopolymerization initiator (D) can be used together with the photoinitiating aid (D-1). When the photopolymerization initiator (D) is used together with the photoinitiation aid (D-1), the colored photosensitive resin composition can have improved sensitivity, thereby improving productivity.

In particular, the photoinitiator (D-1) can be selected from free amines, carboxylic acids, and thiol groups. A group of organic sulfur compounds and mixtures thereof.

Examples of the amine may include aliphatic amines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; and aromatic amines such as methyl 4-dimethylaminobenzoate and 4-dimethylaminobenzene. Ethyl formate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-di Methyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone) and 4,4'-bis(diethylamino)diphenyl Ketone. Aromatic amines are preferred.

The carboxylic acid may include an aromatic heteroacetic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene. Sulfuric acid, dimethoxyphenyl sulfuric acid, chlorophenyl sulfuric acid, dichlorophenyl sulfuric acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine Acid and naphthoxyacetic acid.

Examples of the organic sulfur-containing compound having a thiol group may include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-gin (3-mercaptobutyl) -oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane ginseng (3-mercaptopropionate), isopenic tetra Alcohol (3-mercaptobutyrate), pentaerythritol bismuth (3-mercaptopropionate), diisopentaerythritol hexa(3-mercaptopropionate) and tetraethylene glycol bis(3-mercaptoproperate) Acid ester).

The content of the photopolymerization initiator (D) is preferably from 0.1 to 40% by weight, more preferably from 1 to 30% by weight, based on the total solid content of the binder resin (B) and the photopolymerizable monomer (C). When the amount of the photopolymerization initiator is in the range of 0.1 to 40% by weight, the colored photosensitive resin composition of the present invention can have high sensitivity, thereby shortening the exposure time, thereby improving productivity and maintaining high resolution. In addition, the composition provides sufficient pixel intensity and good smoothness on the surface of the pixel.

Further, when the photoinitiator aid (D-1) is used, the content thereof is preferably from 0.1 to 50% by weight, more preferably, based on the total solid content of the binder resin (B) and the photopolymerizable monomer (C). 1 to 40% by weight. When the amount of the photoinitiating aid is in the range of 0.1 to 50% by weight, the colored photosensitive resin composition of the present invention can have more improved sensitivity and increase the formation of the use composition. The productivity of the color filter.

Antioxidant (E)

In one embodiment of the invention, the antioxidant (E) comprises a mixture of a phenol-based antioxidant and a sulfur-based antioxidant. The use of a mixture of a phenol-based antioxidant and a sulfur-based antioxidant exhibits an enhanced effect as compared to the use of a separate antioxidant.

Examples of the phenol-based antioxidant may include 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propanyloxy]-1,1- Dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane (ADEKASTAB AO-80 from ADEKA, Sumilizer GA-80 from Sumitomo Chemical), isovalerol 肆[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propionate (IRGANOX 1010 from BASF, ADEKASTAB AO-60 from ADEKA, Sumilizer BP-101 from Sumitomo Chemical), 1,3,5-three Methyl-2,4,6-gin (3'5'-di-t-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330 from BASF, ADEKASTAB AO-330 from ADEKA), triethylene glycol-double [3-(3-Tertiary-5-methyl-4-hydroxyphenyl)propionate] (ADGANSTAB AO-70 of IRGFOX245 and ADEKA of BASF), 4,4'-thiol double (6- Tert-butyl-3-methylphenol) (Sumilizer WX from Sumitomo Chemical), gins-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate (IRGANOX 3114 from BASF) , ADEKASTAB AO-20) of ADEKA, 1,6-hexanediol-bis[3-(3,-di-t-butyl-4-hydroxyphenyl)propionate] (IRGANOX259 of BASF), double [ 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoic acid] 2,2-thio-diethyl ester (IRGFOX 1035 from BASF) , N, N'-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamylamine) (IRGANOX 1098 from BASF), 2,4-bis[(octylthio) Methyl]-o-cresol (IRGANOX 1520L from BASF), octadecyl-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (IRGANOX1076 from BASF, ADEKASTAB from ADEKA) AO-50, Sumitomo Chemical's Sumilizer BP-76), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol) (ADEKASTAB AO-40 from ADEKA, Sumilizer BBM from Sumitomo Chemical) 1,1,3-glycol (2-methyl-4-hydroxy-5-third Butylphenyl)butane (ADEKASTAB AO-30 of ADEKA), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX565 from BASF), 4,6-bis(dodecylthiomethyl)-o-cresol (IRGANOX 1726 from BASF), 2-t-butyl-6-( 3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (Sumilizer GM from Sumitomo Chemical), 2-[1-(2-hydroxy-3,5- Di-t-amylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate (Sumilizer GS from Sumitomo Chemical), hybrid 6-[3-(3-tert-butyl- 4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenzo[d,f][1,3,2]dioxaphosphorane Cyclobutane (Sumilizer GP from Sumitomo Chemical).

Examples of sulfur-based antioxidants may include di-dodecyl 3,3'-thiodipropionate (IRGANOX PS 800 FD from BASF), di-octadecyl 3,3'-thiodipropionate (IRGANOX PS 802 FD from BASF), di-tridecyl thiodipropionate (ADEKASTAB AO-503 from ADEKA), 肆-(p-pentyl-thiopropionate) (ADEKA) ADEKASTAB AO-412S), 3,3'-dilauroyl dithiolate (Sumilizer TPL-R from Sumitomo Chemical), di-tetradecyl 3,3'-thiodipropionate (Sumilizer from Sumitomo Chemical) TPM), di-octadecyl 3,3'-thiodipropionate (Sumilizer TPS from Sumitomo Chemical), barium pentaerythritol (3-laurylthiopropionate) (Sumilizer TPD from Sumitomo Chemical) 3,3'-dis-tridecyl thiodipropionate (Sumilizer TL from Sumitomo Chemical), 2-mercaptobenzimidazole (Sumilizer MB from Sumitomo Chemical).

The colored photosensitive resin composition of the present invention uses a mixture of a phenol-based antioxidant and a sulfur-based antioxidant, thereby improving heat resistance and providing high brightness.

The antioxidant (E) content is preferably from 5 to 75 parts by weight based on 100 parts by weight of the solid content of the photopolymerization initiator (D). When the amount of the antioxidant is in the range of 5 to 75 parts by weight, heat resistance can be improved and high brightness can be obtained.

Solvent (F)

In one embodiment of the present invention, the solvent (F) may be any solvent which can disperse or dissolve other components contained in the coloring photosensitive resin composition of the present invention. Especially ethers, aromatic hydrocarbons, ketones, alcohols, esters and decylamines are preferred.

For example, the solvent (F) may include ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; diethylene glycol II An alkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetate, such as methyl ethylene Alcoholic acid diethyl ether and ethyl glycol ethylene ether acetate; alkylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl Acetyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl iso Butyl ketone and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerol; and esters such as ethyl 3-ethoxypropionate, 3- Methyl methoxypropionate and a cyclic ester such as γ-butyrolactone.

The solvent (F) may preferably be an organic solvent having a boiling point of from 100 to 200 ° C, more preferably an alkylene glycol alkyl ether acetate, a ketone or an ester (such as ethyl 3-ethoxypropionate). And methyl 3-methoxypropionate), even more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate and 3-methoxy Methyl propionate. The above solvents may be used singly or in combination of two or more.

The solvent (F) content is preferably from 60 to 90% by weight, more preferably from 70 to 85% by weight, based on the total weight of the coloring photosensitive resin composition of the present invention. When the amount of the solvent (F) is 60 to 90% by weight In the range of the coating, a coating machine such as a roll coater, a spin coater, a slit and a spin coater, a slit coater (also referred to as a "die coater"), and an ink jet can be used to obtain a good coating.

The colored photosensitive resin composition according to an embodiment of the present invention may further contain other polymers, a hardener, a surfactant, an adhesion promoter, a UV absorber, an anti-coagulant, and the like, as necessary.

Examples of other polymers may include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylic acid. Esters, polyesters and polyurethanes.

Hardeners are used to increase deep hardening and mechanical strength. Examples of the hardener may include an epoxy resin, a polyfunctional isocyanate, melamine, and oxetane.

Examples of the epoxy resin may include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolak type epoxy resin, other aromatic Group epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine resin; brominated derivatives of such epoxy resins; aliphatic and alicyclic groups other than epoxy resins and brominated derivatives Or aromatic epoxy compound; epoxidized butadiene (co)polymer; epoxidized isoprene (co)polymer; glycidyl (meth) acrylate (co)polymer; and isocyanuric acid Glyceride.

Examples of the oxetane may include carbonate dioxetane, xylene dioxetane, adipate dioxetane, terephthalate dioxetane And cyclohexanedicarboxylic acid dioxetane.

The hardener can be used in conjunction with a hardening aid which induces ring opening polymerization of the epoxy resin or oxetane. Examples of the hardening aid may include a polycarboxylic acid, a polycarboxylic acid anhydride, and an acid generator.

The polycarboxylic acid anhydride may be a commercially available epoxy resin hardener product such as ADEKAHADONA EH-700 (ADK Industries), RIKACID HH (NJC) and MH-700 (NJC).

The above hardeners may be used singly or in combination of two or more.

The surfactant is used to enhance the coating forming characteristics of the coloring photosensitive resin composition of the present invention, and may include a surfactant based on fluorine and cerium.

Examples of ruthenium-based surfactants may include commercially available products such as DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 (Dow Corning Toray Silicone) as well as TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460. And TSF-4452 (GE Toshiba Silicones). Examples of fluorine-based surfactants may include commercially available products such as MEGAFACE F-470, F-471, F-475, F-482, and F-489 (Dainippon Ink and Chemical Industry).

The above surfactants may be used singly or in combination of two or more.

Examples of the adhesion promoter may include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidol Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropyl Methyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-isocyanatepropyltrimethoxy Base decane and 3-isocyanate propyl triethoxy decane.

The above adhesion promoter may be used singly or in combination of two or more. The content of the adhesion promoter may preferably be from 0.01 to 10% by weight, more preferably from 0.05 to 2% by weight, based on the total solid content of the photosensitive resin composition of the present invention.

Examples of the UV absorber may include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone.

Examples of the anti-coagulant may include sodium polyacrylate.

The colored photosensitive resin composition according to an embodiment of the present invention can be produced by the following method. For example, the colorant (A) is mixed with the solvent (F), and the mixture is dispersed using a bead mill until the average diameter of the colorant is about 0.2 μm or less. If necessary, mix Pigment dispersant or some or all of the binder resin (B). Adding the remaining binder resin (B), photopolymerizable monomer (C), photopolymerization initiator (D) and other components to the mixed dispersion (also referred to as "lacquer"), and if necessary, further adding The solvent is used to obtain a desired concentration, whereby a colored photosensitive resin composition is prepared.

One embodiment of the present invention relates to a color filter formed by using the above-described colored photosensitive resin composition. A color filter according to an embodiment of the present invention includes a colored layer formed by coating a colored photosensitive resin composition on a substrate, followed by exposure and development to form a pattern.

Hereinafter, a method of forming a pattern using the colored photosensitive resin composition of the present invention will be described in detail.

The method of forming a pattern using the colored photosensitive resin composition of the present invention can be carried out by a method known in the art, and usually includes the steps of coating, exposing and removing. The colored photosensitive resin composition of the present invention is coated on a substrate, followed by photocuring and developing to form a pattern to be used as a black matrix or a colored pixel (colored image).

In the coating step, the colored photosensitive resin composition of the present invention is coated on a substrate (usually used in the art such as, but not limited to, a glass or tantalum wafer) or on a pre-formed layer of the colored photosensitive resin composition, Subsequent drying to remove volatile components, such as solvents, results in a smooth coating film. The coating film preferably has a thickness of from 1 to 3 μm.

In the exposure step, in order to obtain the desired pattern, the coating film is irradiated with UV in some areas using a mask. In order to uniformly illuminate the entire area with parallel rays and to accurately align the mask with the substrate, a mask aligner or stepper is preferably used.

In the removing step, the coating film cured by UV irradiation is contacted with an alkaline aqueous solution to dissolve and develop the unexposed regions, thereby obtaining a desired pattern. After development, if necessary, the drying may be carried out at a temperature of from 150 to 230 ° C for 10 to 60 minutes.

Any developing solution known in the art can be used for development. In particular, an aqueous solution containing a basic compound and a surfactant can be used.

The basic compound may be an inorganic or organic basic compound. Examples of the inorganic basic compound may include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium citrate, potassium citrate, carbonic acid. Sodium, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia. Examples of the organic basic compound may include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine and ethanolamine. These inorganic and organic basic compounds may be used singly or in combination of two or more. The basic compound content may be from 0.01 to 10 parts by weight, preferably from 0.03 to 5 parts by weight, based on the total weight of the developing solution.

The surfactant can be a nonionic, anionic or cationic surfactant. Examples of the nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, and other polyoxyethylene derivatives, ethylene oxide-propylene oxide blocks. Copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine. Examples of anionic surfactants may include higher carbon number alcohol sulfates such as sodium lauryl sulfate and sodium oleyl sulfate; alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkylarylsulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. Examples of the cationic surfactant may include an amine and a quaternary ammonium salt such as octadecylamine hydrochloride and lauryl trimethylammonium chloride. These surfactants may be used singly or in combination of two or more. The surfactant content may be from 0.01 to 10 parts by weight, more preferably from 0.05 to 8 parts by weight, even more preferably from 0.1 to 5 parts by weight, based on the total weight of the developing solution.

As mentioned above, the colored photosensitive resin composition is coated, dried, exposed to be patterned and developed to obtain a pixel or a black matrix corresponding to each color of the coloring material in the photosensitive resin composition, and according to the color filter required The number of colors repeats the procedures, thereby obtaining a color filter. The construction and preparation of color filters are known in the art, and thus are omitted herein. A detailed description.

One embodiment of the present invention relates to a liquid crystal display device having the above-mentioned color filter.

The liquid crystal display device of the present invention has the above-mentioned color filter and includes other components known in the art. That is, any liquid crystal display device to which the color filter of the present invention can be applied is included in the present invention. For example, there is a transmissive liquid crystal display device in which an opposite electrode substrate having a thin film transistor (TFT), a pixel electrode, and an alignment layer face each other at a predetermined interval, and a liquid crystal material is introduced into the space to form a liquid crystal layer. Further, a reflective liquid crystal display device having a reflective layer between the color filter substrate and the coloring layer may be mentioned. Further, a liquid crystal display device comprising a thin film transistor (TFT) substrate combined on a transparent electrode of a color filter and a backlight fixed at a position of the TFT substrate overlapping the color filter may be mentioned.

The invention is further illustrated by the following examples, comparative examples and experimental examples, which should not be construed as limiting the scope of the invention.

Examples 1 to 2 and Comparative Examples 1 to 4: Preparation of Colored Photosensitive Resin Compositions

The colored photosensitive resin composition was prepared by mixing the components (unit: weight%) listed in Table 1 below.

The components of Table 1 above are as follows.

Colorant (A)

A-1: C.I. Pigment Red 254

A-2: Acid Red 94 (TCI)

Adhesive resin (B)

B-1: copolymer of methacrylic acid and benzyl methacrylate (molar ratio of methacrylic acid unit to benzyl methacrylate unit: 31:69; acid value: 105; weight average molecular weight: 30,000)

Photopolymerizable monomer (C)

C-1: diisopentyltetraol hexaacrylate (KAYARAD DPHA, Nippon Kayaku)

Photopolymerization initiator (D)

D-1: OXE-01 (Ciba)

Antioxidant (E)

E-1: phenol-based antioxidant AO-60 (ADEKA)

E-2: Sulfur-based antioxidant AO-412S (ADEKA)

E-3: Sulfur-based antioxidant AO-503 (ADAKA)

E-4: Hybrid Antioxidant Sumilizer GP (Sumitomo Chemical)

Solvent (F)

F-1: propylene glycol monomethyl ether acetate

F-2: ethyl 3-ethoxypropionate

Additive (G)

G-1: 矽 based surfactant (SH-8400)

G-2: pigment dispersant

G-3: adhesion promoter (3-methacryloxypropyltrimethoxydecane)

Experimental Example 1: Evaluation of brightness and heat resistance

The colored photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4 were used to prepare a color filter. Specifically, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, and the glass substrate was placed on a hot plate maintained at a temperature of 100 ° C for 3 minutes to form a film on the glass substrate. Subsequently, a test light mask having a line/space pattern of 1 to 50 μm and a pattern of gradually varying transmittance in the range of 1 to 100% was placed on the film, and the UV irradiation was performed at 100 mJ/cm ² using a 1 KW high pressure mercury lamp. The film and the light mask are arranged at intervals of 100 μm without any special optical filter, and the mercury lamp contains all g, h and i rays. The UV-irradiated film was immersed in an aqueous KOH solution (pH 10.5) used as a developing solution for 2 minutes. After development, the film was washed with distilled water and dried with nitrogen, followed by heating in an oven set at 220 ° C for 1 hour to obtain a color filter. The obtained color filter was confirmed to have a thickness of 2.0 μm.

The color filter prepared above was evaluated for its brightness and heat resistance by the following method. The results are shown in Table 2.

(1) Brightness (Y)

The brightness and color coordinates of the colored layer were measured using a microspectrophotometer OSP-SP2000.

O: more than 17.8, △: 17.6 to 17.8, X: less than 17.6

(2) Heat resistance

After heating the color filter in an oven set at 230 ° C for 2 hours, the color change (ΔEab) was measured, and the change in luminance (ΔY) was confirmed.

△Eab

O: less than 3, △: 3 to 4, X: more than 4

△Y

O: less than 0.3, △: 0.3 to 0.5, X: more than 0.5

(Rx=0.656, Ry=0.323 standard)

As shown in Table 2, the present invention using a mixture of a phenol-based antioxidant and a sulfur-based antioxidant as compared to Comparative Examples 1 to 4 using either a phenol-based antioxidant and a sulfur-based antioxidant The colored photosensitive resin composition has excellent heat resistance and exhibits small brightness change and high brightness after additional heating.

While a particular embodiment of the invention has been shown and described, it will be understood by those skilled in the art Make various changes and modifications.

Accordingly, the scope of the invention is defined by the scope of the appended claims and their equivalents.

Claims (8)

A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E), and a solvent (F), The colorant (A) comprises one or more dyes and the antioxidant (E) comprises a mixture of a phenol-based antioxidant and a sulfur-based antioxidant. The colored photosensitive resin composition of claim 1, wherein the colorant (A) comprises one or more red dyes. The colored photosensitive resin composition of claim 1, wherein the colorant (A) further comprises a pigment. The colored photosensitive resin composition of claim 1, wherein the colorant (A) is contained in an amount of from 5 to 70% by weight based on the total solid content of the colored photosensitive resin composition. The colored photosensitive resin composition of claim 4, wherein the dye content is from 1 to 60% by weight based on the total solid content of the colorant (A). The colored photosensitive resin composition of claim 1, wherein the antioxidant (E) content is 5 to 75 parts by weight based on 100 parts by weight of the solid content of the photopolymerization initiator (D). A color filter formed by using the colored photosensitive resin composition according to any one of claims 1 to 6. A liquid crystal display device having the color filter of claim 7.