KR20150015098A - Colored Photosensitive Resin Composition, Color Filter, and Liquid Crystal Display Device Having the Same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, which includes (A) a coloring agent; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerizable initiator; (E) an antioxidant; and (F) a solvent wherein the (A) coloring agent has at least one dye and the (E) antioxidant is used in a mixture of a phenol based antioxidant and a sulfur based antioxidant, a color filter formed by using the same and a liquid crystal display device with the color filter. The colored photosensitive resin composition in the present invention has a good heat resistance and an outstanding brightness.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter and a liquid crystal display device having the same, and more particularly, to a colored photosensitive resin composition which is excellent in heat resistance and can exhibit excellent brightness even after high- And a liquid crystal display device provided with the color filter.

BACKGROUND ART [0002] Color filters are widely used in imaging elements, liquid crystal displays (LCDs), and the like, and the application range thereof has been expanded. The color filter is usually prepared by uniformly applying a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern-formed, exposing and developing a coating film formed by heating and drying, And repeating an operation of heating and curing as needed, for each color to form pixels of each color.

As the colored photosensitive resin composition used at this time, a composition containing a photopolymerizable monomer and a photopolymerization initiator together with a pigment and a binder resin is widely used, and a photosensitive resin composition containing a black pigment is also used for forming a black matrix.

Korean Patent Laid-Open 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, a photopolymerization initiator, a pigment, an antioxidant and a solvent , A mixture of a first antioxidant selected from the group consisting of a quinolone compound, an amine compound, a phenol compound, and a mixture thereof and a second antioxidant comprising a phosphite compound as an antioxidant to form a photosensitive resin composition Oxidation can be prevented and thermal stability can be improved.

However, a color filter prepared using a photosensitive resin composition containing only a pigment has been studied for a photosensitive resin composition containing a dye for improving brightness because of low brightness, but when a dye is used, heat resistance is low, There was a problem.

An object of the present invention is to provide a colored photosensitive resin composition which is excellent in heat resistance and can exhibit excellent color with little color change even after a high temperature process.

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

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

On the other hand, the present invention includes a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) And at least one dye, wherein the antioxidant (E) provides a colored photosensitive resin composition using a phenol-based antioxidant and a sulfur-based antioxidant.

On the other hand, the present invention provides a color filter formed using the colored photosensitive resin composition.

On the other hand, the present invention provides a liquid crystal display device provided with the color filter.

The colored photosensitive resin composition according to the present invention has a color filter exhibiting a high luminance by using a mixture of a phenol-based antioxidant and a sulfur-based antioxidant as an antioxidant even though it contains at least one dye having low heat resistance as a colorant Can be effectively used for manufacturing.

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

An embodiment of the present invention includes a colorant (A), a binder resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), an antioxidant (E) and a solvent (F) (E) is a colored photosensitive resin composition comprising a phenol-based antioxidant and a sulfur-based antioxidant in admixture.

The colorant (A)

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

The dye can be used without limitation as long as it is used in the art such as cyan, azanthene, azo, anthraquinone, metal complex, quinoline, pyrazolone and the like.

The colorant (A) may further comprise one or more pigments in addition to the dye.

As the pigment, an organic pigment which is a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists) or an inorganic pigment which is a metal oxide, a metal complex salt and an inorganic salt of barium sulfate can be used, It is preferable to use an organic pigment in view of excellent heat resistance and color development.

The compounds categorized as pigments in the color index (published by The Society of Dyers and Colourists) include, but are not necessarily limited to, pigments having a color index (C.I.) number as follows.

C.I. 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;

C.I. Pigment Orange 13, 31, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. 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-exemplified colorants, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment Red 254, and the like.

The above-exemplified colorants may be used alone or in combination of two or more. For example, in order to form red pixels among the above-mentioned coloring agents, C.I. Pigment Red 254 and C.I. Pigment Red 177. < / RTI >

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

The amount of the dye is preferably 5 to 100% by weight, more preferably 1 to 60% by weight based on the amount of the colorant (A). When the dye is included in an amount of 1 to 60% by weight, a sufficient pattern is obtained due to excellent luminance, and a high quality color filter pattern can be formed

The binder resin (B)

In one embodiment of the present invention, it is preferable that the binder resin (B) is a copolymer of a monomer having a carboxyl group and another monomer copolymerizable therewith.

The other copolymerizable monomer is a monomer having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene,? -Methylstyrene and vinyltoluene; Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, Unsaturated carboxylate compounds such as acrylate; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and? -Chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, Methyl-3-acryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, Unsaturated oxetanecarboxylate compounds, and the like. These monomers may be used alone or in combination of two or more.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the binder resin (B) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the molecular weight distribution of the binder resin is 1.5 to 6.0, the binder resin is preferable because of its excellent developability.

The content of the binder resin (B) is preferably in the range of 5 to 90% by weight, more preferably 10 to 70% by weight based on the total solid content of the colored photosensitive resin composition of the present invention. When the content of the binder resin is in the range of 5 to 90% by weight, solubility in a developing solution is sufficient, so that development residue is not easily generated on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion is difficult to occur. It is preferable since the leakage tendency tends to be good.

The photopolymerizable monomer (C)

In one embodiment of the present invention, the photopolymerizable monomer (C) is a monomer that can be polymerized by an active radical, acid, or the like generated from a photopolymerization initiator by light irradiation.

Specific examples of the photopolymerizable monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, Acrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol tetraacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 2-butanediol dimethacrylate, 1, 2-butanediol dimethacrylate, , 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like. .

The photopolymerizable monomer (C) is preferably contained in an amount of 5 to 45% by weight, more preferably 10 to 35% by weight based on the solid content in the colored photosensitive resin composition of the present invention. When the content of the photopolymerizable monomer is within the range of 5 to 45% by weight, it is preferable that the strength and smoothness of the pixel portion are improved.

Photopolymerization initiator (D)

In one embodiment of the present invention, the photopolymerization initiator (D) can be used without any particular limitation as long as it can polymerize the binder resin (B) and the photopolymerizable monomer (C). In particular, it is preferable to use at least one compound selected from the group consisting of a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound and an oxime compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, desirable.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2,6-dichlorophenyl) - 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 . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, compounds represented by the following formulas (1) to (3), and the like.

[Chemical Formula 1]

(2)

(3)

Further, other photopolymerization initiators conventionally used in the art may be further used insofar as the effects of the present invention are not impaired. Examples of other photopolymerization initiators include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and anthracene-based compounds, and these may be used alone or in combination of two or more.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxyanthracene. have.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, methyl phenylchloroxylate, Titanocene compounds and the like can be mentioned as other photopolymerization initiators.

The photopolymerization initiator (D) may be used in combination with a photopolymerization initiator (D-1). When the photopolymerization initiator (D) is used in combination with the photopolymerization initiator (D-1), the photosensitive resin composition containing the photopolymerization initiator (D)

As the photopolymerization initiation auxiliary (D-1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amines such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl aminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- Ethylamino) benzophenone, and the like. As the amine compound, an aromatic amine compound is preferably used.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, And aromatic heteroacetic acids such as dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) Triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate). .

The amount of the photopolymerization initiator (D) to be used is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight based on the total amount of the binder resin (B) and the photopolymerizable monomer (C) Weight%. When the photopolymerization initiator is in the range of 0.1 to 40% by weight, the colored photosensitive resin composition of the present invention has high sensitivity and shortens the exposure time, thereby improving productivity and maintaining high resolution. The strength of the pixel portion and the smoothness on the surface of the pixel portion become favorable.

When the photopolymerization initiator auxiliary (D-1) is used, the amount of the photopolymerization initiator auxiliary (D-1) to be used is preferably in the range of 0.1 to 5 parts by weight, Is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight. When the amount of the photopolymerization initiator is within the range of 0.1 to 50% by weight, the sensitivity of the colored photosensitive resin composition of the present invention is higher and the productivity of the color filter formed using the composition is improved.

Antioxidant (E)

In one embodiment of the present invention, the antioxidant (E) is a mixture of a phenol antioxidant and a sulfur antioxidant. By using these phenol antioxidants and sulfur antioxidants in combination, a synergistic effect can be obtained when used alone.

Examples of the phenolic antioxidant include 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- 2,4,8,10-tetraoxaspiro [5.5] undecane (Adekastab AO-80 manufactured by ADEKA, Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl tetrakis [3- (IRGANOX1010 manufactured by BASF Corporation, Adekastab AO-60 manufactured by ADEKA Corporation, Sumilizer BP-101 manufactured by Sumitomo Chemical Co., Ltd.), 1,3,5-trimethyl- Bis (3'5'-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX1330 manufactured by BASF, Adekastab AO- 330 manufactured by ADEKA), triethylene glycol- (IRGANOX245 manufactured by BASF, Adekastab AO-70 manufactured by ADEKA), 4,4'-thiobis (6-t-butyl-3 -Methylphenol) (Sumilizer WX manufactured by Sumitomo Chemical Co., Ltd.), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 259 manufactured by BASF), 1,6- (IRGANOX1035 manufactured by BASF), N, N'-hexamethylenebis (3,3-di-t-butyl-4-hydroxyphenyl) propionate, Bis (octylthio) methyl] -o-cresol (IRGANOX 1520L, manufactured by BASF), octadecyl- [ (IRGANOX1076 manufactured by BASF Corporation, Adekastab AO-50 manufactured by ADEKA Corporation, Sumilizer BP-76 manufactured by Sumitomo Chemical Co., Ltd.), 4,4 (di-t-butyl-4-hydroxyphenyl) propionate -Butylidene-bis (3-methyl-6-t-butylphenol) (Adekastab AO-40 manufactured by ADEKA, Sumilizer BBM manufactured by Sumitomo Chemical Co., Ltd.), 1,1,3- (Adekastab AO-30 manufactured by ADEKA), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di -t-butyl anilino) -1,3,5-triazine (manufactured by BASF Corp. (IRGANOX565), 4,6-bis (dodecylthiomethyl) -o-cresol (IRGANOX1726 manufactured by BASF), 2-t-butyl- 4-methylphenylacrylate (Sumilizer GM manufactured by Sumitomo Chemical Co., Ltd.), 2- [1- (2-hydroxy-3,5-di- Acrylate (Sumilizer GS manufactured by Sumitomo Chemical Co., Ltd.), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10- Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphperin (Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd.).

 Examples of the sulfur-based antioxidant include, for example, titanyl dodecyl 3,3'-thiodipropionate (IRGANOX PS 800 FD from BASF), dioctadecyl 3,3'-thiodipropionate (IRGANOX PS 802 from BASF) FD), ditridecylthiodipropionate (Adekastab AO-503 manufactured by ADEKA), pentaerythritol-tetrakis- (β-lauryl-thiopropionate) (Adekastab AO-412S manufactured by ADEKA) , Dilauryl-3,3'-thiodipropionate (Sumilizer TPL-R manufactured by Sumitomo Chemical Co., Ltd.), dimyristyl-3,3'-thiodipropionate (Sumilizer TPM manufactured by Sumitomo Chemical Co., Ltd.) (Sumilizer TPS manufactured by Sumitomo Chemical Co., Ltd.), pentaerythritol tetrakis (3-laurylthiopropionate) (Sumilizer TPD manufactured by Sumitomo Chemical Co., Ltd.), di Tridecyl-3,3'-thiodipropionate (Sumilizer TL manufactured by Sumitomo Chemical Co., Ltd.), 2-mercaptobenzimidazole Mocha and the like can be manufactured by Sumitomo Chemical riser MB).

According to the present invention, by mixing the phenol-based antioxidant and the sulfur-based antioxidant in combination, it is possible to enhance the heat resistance of the colored photosensitive resin composition of the present invention and to exhibit excellent brightness

The antioxidant (E) is preferably used in an amount of 5 to 75 parts by weight based on 100 parts by weight 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 enhanced and excellent brightness can be exhibited.

Solvent (F)

In one embodiment of the present invention, the solvent (F) may be used without particular limitation insofar as it is effective in dispersing or dissolving the other components contained in the colored photosensitive resin composition of the present invention. In particular, ethers, aromatic hydrocarbons Ketones, alcohols, esters, amides and the like are preferable.

Specific examples of the solvent (F) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol mono Alkylene glycol alkyl ether acetates such as methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene , Methyl ethyl ketone , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, 3- Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.

Among the solvents exemplified above, organic solvents having a boiling point of 100 to 200 DEG C are preferably used in view of the coating property and the drying property, more preferably alkylene glycol alkyl ether acetates, ketones, 3-ethoxy Propylene glycol monomethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and the like. Methyl propoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent (F) is preferably 60 to 90% by weight, and more preferably 70 to 85% by weight based on the total amount of the colored photosensitive resin composition of the present invention. When the content of the solvent is in the range of 60 to 90% by weight, the coating property tends to be improved when the coating composition is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (also referred to as a die coater) Therefore, it is preferable.

In addition to the above-described components, the colored photosensitive resin composition according to one embodiment of the present invention may also contain additives such as other polymer compounds, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an anti-

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

The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent 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 Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than glycidyl ester resins, glycidyl amine resins or brominated derivatives of such epoxy resins, epoxy resins and their brominated derivatives ) Polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidylisocyanurate.

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 agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. 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 agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.).

The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used to further improve the film-forming property of the colored photosensitive resin composition of the present invention, and a fluorine-based surfactant, a silicone-based surfactant, or the like may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF- 4460, and TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of preferably 0.01 to 10% by weight, more preferably 0.05 to 2% by weight based on the solid content of the photosensitive resin composition of the present invention.

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 colored photosensitive resin composition according to one embodiment of the present invention can be produced, for example, by the following method.

The colorant (A) is mixed with the solvent (F) in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant is about 0.2 탆 or less. At this time, a pigment dispersant may be used if necessary, and some or all of the binder resin (B) may be blended. After the addition of the remainder of the binder resin (B), the photopolymerizable monomer (C) and the photopolymerization initiator (D) and other components as required, is added to the obtained dispersion (hereinafter also referred to as a mill base) The desired colored photosensitive resin composition can be obtained by further adding an additional solvent so as to have a predetermined concentration.

One embodiment of the present invention relates to a color filter formed using the above-mentioned colored photosensitive resin composition. A color filter according to an embodiment of the present invention is characterized by including a colored layer formed by applying the above-mentioned colored photosensitive resin composition on a substrate, and exposing and developing in a predetermined pattern.

Hereinafter, the pattern forming method 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 may be a method known in the art, An exposure step; And a removing step. The colored photosensitive resin composition of the present invention is applied onto a substrate and then subjected to photo-curing and development to form a pattern, so that it can be used as a black matrix or a colored pixel (colored image).

In the application step, the colored photosensitive resin composition of the present invention is applied on a substrate (not limited to a glass or silicon wafer in general) or a previously formed colored photosensitive resin composition layer and preliminarily dried to remove volatile components such as a solvent, . At this time, the thickness of the coating film is preferably 1 to 3 mu m.

The exposure step is a step of irradiating ultraviolet rays to a specific region through a mask to cure the coating film to obtain a desired pattern. At this time, it is preferable to use a mask aligner, a stepper, or the like so as to uniformly irradiate the entire exposed portion with a parallel light beam and accurately position the mask and the substrate.

The removing step is a step of obtaining a desired pattern by irradiating ultraviolet rays to bring the coated film, which has been cured, into contact with an alkali aqueous solution to dissolve and expose the non-exposed region. After development, if necessary, post-drying may be performed at about 150 to 230 DEG C for about 10 to 60 minutes.

Any developer known in the art may be used for the development, but preferably an aqueous solution containing an alkaline compound and a surfactant can be used.

The alkaline compound may be an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The alkaline compound may be contained in an amount of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on the developing solution.

The surfactant may be selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant, or a mixture thereof. 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. 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, alkylsulfuric acid salts such as sodium lauryl sulfate and ammonium lauryl sulfate, dodecylbenzenesulfonic acid And alkylarylsulfonic acid salts such as sodium or sodium dodecylnaphthalenesulfonate. Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more. The amount of the surfactant is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, and even more preferably 0.1 to 5 parts by weight based on the developer.

A pixel or a black matrix corresponding to the color of the coloring material in the photosensitive resin composition is obtained through the operation of coating, drying, patterning exposure, and development of the colored photosensitive resin composition as described above. The color filter can be obtained. The configuration and manufacturing method of the color filter are well known in the art and will not be described in detail.

One embodiment of the present invention relates to a liquid crystal display provided with the above-described color filter.

The liquid crystal display device of the present invention includes configurations known in the art, except that the liquid crystal display device is provided with the color filter described above. That is, all liquid crystal display devices to which the color filter of the present invention can be applied are included in the present invention. For example, a transmissive liquid crystal display device in which a counter electrode substrate having a thin film transistor (TFT element), a pixel electrode, and an alignment layer are faced at predetermined intervals and a liquid crystal material is injected into the gap portion to form a liquid crystal layer . There is also a reflective liquid crystal display device in which a reflective layer is provided between the substrate of the color filter and the colored layer. As another example, a thin film transistor (TFT) substrate integrated on a transparent electrode of a color filter and a liquid crystal display device including a backlight fixed to a position where a TFT substrate overlaps a color filter can be given.

Hereinafter, the present invention will be described more specifically with reference to Examples, Comparative Examples and Experimental Examples. It should be apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Examples 1 to 2 and Comparative Examples 1 to 4: Preparation of colored photosensitive resin composition

Each of the components was mixed at a ratio (unit: wt%) as shown in Table 1 below to prepare a colored photosensitive resin composition.

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 coloring agent A-1 3.94 3.94 3.94 3.94 3.94 3.94 A-2 0.82 0.82 0.82 0.82 0.82 0.82 Binder resin B-1 3.56 3.56 3.56 3.56 3.56 3.56 Photopolymerization
Monomer C-1 3.56 3.56 3.56 3.56 3.56 3.56 Light curing
Initiator D-1 1.1 1.1 1.1 1.1 1.1 1.1 Antioxidant E-1 0.205 0.205 0.41 E-2 0.205 0.205 0.41 E-3 0.41 E-4 0.41 solvent F-1 70 70 70 70 70 70 F-2 15 15 15 15 15 15 additive G-1 1.5 1.5 1.5 1.5 1.5 1.5 G-2 0.1 0.1 0.1 0.1 0.1 0.1 G-3 0.01 0.01 0.01 0.01 0.01 0.01

The components used in Table 1 are as follows.

The colorant (A)

A-1: C.I. Pigment Red 254

A-2: Acid Red 94 (manufactured by TCI)

The binder resin (B)

B-1: Copolymer of methacrylic acid and benzyl methacrylate having a molar ratio of methacrylic acid unit to benzyl methacrylate unit of 31:69, a weight average molecular weight of 30,000, and an acid value of 105

The photopolymerizable monomer (C)

C-1: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator (D)

D-1: OXE-01 (manufactured by Ciba)

Antioxidant (E)

E-1: phenolic antioxidant AO-60 (manufactured by Adeka)

E-2: Sulfur-based antioxidant AO-412S (manufactured by Adeka)

E-3: Sulfur-based antioxidant AO-503 (manufactured by Adeka)

E-4: Mixed type antioxidant Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.)

Solvent (F)

F-1: Propylene glycol monomethyl ether acetate

F-2: Ethyl 3-ethoxypropionate

Additive (G)

G-1: Silicone surfactant (SH-8400)

G-2: Pigment dispersant

G-3: adhesion promoter (3-methacryloxypropyltrimethoxysilane)

Experimental Example 1: Evaluation of luminance and heat resistance

A color filter was prepared using the colored photosensitive resin compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4. Specifically, each of the colored photosensitive resin compositions was coated on a glass substrate by spin coating, then placed on a heating plate, and held at a temperature of 100 캜 for 3 minutes to form a thin film. Then, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner and a line / space pattern of 1 μm to 50 μm was placed on the thin film, and the distance from the test photomask was set to 100 μm Ultraviolet rays were irradiated. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 220 ° C for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 탆.

The luminance and heat resistance of the color filter thus produced were evaluated by the following methods, and the results are shown in Table 2 below.

(1) Brightness (Y)

The luminance and chromaticity coordinates of the formed colored layer were measured using a microscopic spectrometer OSP-SP2000.

?: More than 17.8,?: 17.6 to 17.8, X: less than 17.6

(2) Heat resistance

The prepared color filter was heated in a heating oven at 230 deg. C for 2 hours, and then the color change (DELTA Eab) before and after heating was measured to confirm the change in brightness (DELTA Y) before and after the heat resistance evaluation.

△ Eab

?: Less than 3,?: 3 to 4, X: more than 4

ΔY

?: Less than 0.3,?: 0.3 to 0.5, X: more than 0.5

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Luminance (Y) ○ ○ △ △ △ △ Heat resistance △ E * ab ○ ○ ○ ○ ○ ○ Y ○ ○ △ △ △ △

(Rx = 0.656, Ry = 0.323)

As shown in Table 2 above, the colored photosensitive resin composition of the present invention, in which the phenolic antioxidant and the sulfur antioxidant were mixed, compared to Comparative Examples 1 to 4 using the phenolic antioxidant and the sulfur antioxidant alone It was confirmed that even after the additional heating, the luminance change was small and the luminance was high.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Do. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

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

Claims (8)

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