KR20140113131A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition. More specifically, the present invention relates to a colored photosensitive resin composition comprising a coloring agent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an antioxidant, and a solvent, wherein the photopolymerization initiator includes a compound represented by chemical formula 1, and the antioxidant includes a compound represented by chemical formula 2, a compound represented by chemical formula 3 or a mixture thereof. Therefore, the colored photosensitive resin composition facilitates the formation of a micropattern, increases the taper angle of a pattern to obtain high resolution, and enables the manufacture of a color filter having high luminance.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a colored photosensitive resin composition.

BACKGROUND ART [0002] Color filters are widely used in imaging devices, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device, an image pickup device, or the like is a device for 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- The coating film formed by heating and drying (hereinafter also referred to as preliminary firing) may be exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-firing) may be repeated for each color, Color pixels are formed.

As a production method of a color filter using a conventional pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method, and the like are known. In the case of the pigment dispersion method, a colored photosensitive composition in which a binder resin, a photopolymerization initiator, a photopolymerizable monomer or the like is added to a coloring composition in which a pigment is dispersed by a dispersing agent or the like is coated on a glass substrate and dried, The colored photosensitive resin composition is cured or softened. Next, a coloring pattern is formed by dissolving a portion that has not been cured or a softened portion in the developing process, and a step of fixing the coloring pattern onto the substrate through a heating process is repeated for each color to form a color filter.

The colored photosensitive resin composition used for forming a pixel of such a color filter is required to have sufficient resolution, adhesion with a substrate, and low development residue. In addition, it is required to improve the pixel formability such as sharpness of the pattern edge, that is, sufficient developing margin, that the residue is not formed in the removed portion in the developing process, that the removed portion has sufficient solubility, and the like. Particularly, in recent years, as the substrate becomes larger, the time required for the developing process becomes longer, and a colored photosensitive resin composition having a large developing margin is strongly demanded. When a colored photosensitive resin composition having a small developing margin is used, problems such as loss or erosion of a pixel occur particularly when a time is required for a developing process such as a color filter for a large screen.

In order to solve such a problem, an oxime ester compound is used as a photopolymerization initiator. However, when a pattern is formed using a colored photosensitive resin composition containing an oxime ester-based photopolymerization initiator, only the surface is cured, There is still a problem that sufficient straightness can not be obtained in the case of the above. Korean Patent Laid-Open No. 2009-61268 uses an excessive amount of an initiator for high sensitivity, but causes an insufficient resolution and a luminance drop due to the use of an excessive amount of an initiator.

Korea Patent Publication No. 2009-61268

An object of the present invention is to provide a colored photosensitive resin composition capable of realizing a high taper angle of a pattern.

An object of the present invention is to provide a colored photosensitive resin composition capable of forming a fine pattern.

It is an object of the present invention to provide a colored photosensitive resin composition capable of producing a color filter having high luminance.

1. A composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an antioxidant and a solvent; Wherein said photopolymerization initiator comprises a compound represented by the following general formula (1); Wherein the antioxidant is a colored photosensitive resin composition comprising a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:

[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a cycloalkyl group or an aryl group having 6 to 20 carbon atoms)

 (3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom or A straight or branched chain alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms).

2. The colored photosensitive resin composition according to 1 above, wherein the acid value of the alkali-soluble resin is 20 to 200 mgKOH / g.

3. The positive photosensitive composition as described in 1 above, further comprising at least one photopolymerization initiator selected from the group consisting of acetophenone, benzoin, benzophenone, triazine, oxime, biimidazole and thioxanthone compounds By weight.

4. The colored photosensitive resin composition according to 1 above, wherein the compound represented by Formula 1 is contained in an amount of 10 to 100% by weight based on the total weight of the photopolymerization initiator.

5. The method according to item 1 above, wherein 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4-di-t-butylphenol, Butylphenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4- diisopropylphenol, 2- Octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2- Amylphenol, 2,4-di-t-amylphenol, 6-t-butyl-ocresol, 2,6-di- Butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec- -Cresol, 2-t-octyl-o-cresol, 2-t-dodecyl-p-cresol, 2- Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-thio-bis Butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritoltetrakis [3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5- Benzene, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl- T-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'- -Hydroxyphenylpropionate)] methane. The colored photosensitive resin composition according to claim 1, wherein the antioxidant is at least one selected from the group consisting of:

6. The photosensitive resin composition according to 1 above, wherein the amount of the coloring agent is 5 to 60 wt%, the amount of the alkali-soluble resin is 10 to 80 wt%, the amount of the photopolymerizable compound is 5 to 50 wt% From 0.1 to 30% by weight; The antioxidant is contained in an amount of 1 to 80 parts by weight based on 100 parts by weight of the photopolymerization initiator; Wherein the solvent comprises 10 to 90% by weight of the total weight of the colored photosensitive resin composition.

7. The colored photosensitive resin composition according to 1 above, further comprising at least one photopolymerization initiation auxiliary selected from the group consisting of an amine compound, an alkoxyanthracene compound and a thioxanthone compound.

8. A color filter made of a colored photosensitive resin composition according to any one of the above 1 to 7.

The present invention realizes a taper angle of a pattern at a high level, exhibits a high resolution, and can produce a color filter having a fine pattern.

The present invention can produce a color filter with high luminance.

The present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an antioxidant and a solvent; The photopolymerization initiator comprises a compound represented by the formula (1); Since the antioxidant includes the compound represented by the general formula (2), the compound represented by the general formula (3), or a mixture thereof, it is possible to easily form a fine pattern, realize a high taper angle of the pattern, To a colored photosensitive resin composition capable of producing a filter.

Hereinafter, the present invention will be described in detail.

The colored photosensitive resin composition of the present invention includes a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

<Colorant>

The colorant may be a pigment, a dye or a mixture thereof.

The pigment may be an organic pigment, an inorganic pigment or a mixture thereof, which are commonly used in the art.

The organic pigment is not particularly limited and may be a pigment used for printing ink, inkjet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, anthraquinone pigments, anthraquinone pigments, anthanthrone pigments, anthanthrone pigments, indanthrone pigments, indanthrone pigments, Pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. These may be used alone or in combination of two or more.

The inorganic pigment is not particularly limited and may be a metal compound such as a metal oxide or a metal complex salt and specifically includes a group consisting of iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and carbon black &Lt; / RTI &gt; These may be used alone or in combination of two or more.

Organic pigments and inorganic pigments are compounds classified as pigments in the color index (The Society of Dyers and Colourists), and specifically,

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, 194 and 214; C.I. Pigment Orange 13, 31, 38, 40, 42, C.I. Orange pigments such as Pigment Orange 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264, 265; C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 36, and 58; C.I. Brown pigments such as Pigment Brown 23 and 25; C.I. Pigments such as Pigment Black 1 and Pigment Black 7, and the like. Pigment Yellow 138, 139, 150; C.I. Pigment Red 177, 209, 254; C.I. Pigment Violet 23; C.I. Pigment Blue 15: 6; C.I. Pigment Green 36, and the like. These may be used alone or in combination of two or more.

The dye is not particularly limited as long as it has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance, solvent resistance, etc., for example, an acid dye having an acid group such as a sulfonic acid or a carboxylic acid; Salts of acidic dyes and nitrogen-containing compounds; Sulfonamide forms of acidic dyes and derivatives thereof; Azo dyes, xanthan dyes, phthalocyanine dyes, and derivatives thereof.

Preferably, the dye is a compound classified as a dye in a color index (published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (coloring yarn).

The dye is not particularly limited, and for example, C.I. As solvent dyes, C.I. Yellow dyes such as Solvent Yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94, 98, 99, 151, 162, 163; C.I. Red dyes such as Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146, 179; C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 41, 45, 56, 62; C.I. Blue dyes such as Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70; C.I. Violet dyes such as solvent violet 8, 9, 13, 14, 36, 37, 47, 49; C.I. Green dyes such as Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like. In view of excellent solubility in organic solvents, Solvent Yellow 14, 16, 21, 56, 151, 79, 93; C.I. Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; C.I. Solvent Orange 41, 45, 62; C.I. Solvent Blue 35, 36, 44, 45, 70; C.I. Solvent violet 13, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45, 62 or the like is more preferable.

Also, C.I. CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, Yellow dye; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426; Orange dyes such as C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, , 335, 340 and the like; Violet dyes such as C.I. Acid Violet 6B, 7, 9, 17, 19, 66 and the like; Green dyes such as CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109, Preferably CI Acid Yellow 42; C.I. Acid Red 92; C. I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27, and the like.

As CI direct dyes, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 136, 138, 141 and the like; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; Orange dyes such as C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 , 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293; Violet dyes such as C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; Green dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79,

Also, C.I. Yellow dyes such as C.I. Modatto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 as modaneto dyes; CI Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95; CI Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, dyes; CI Modanito Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 43, 44, 48, 49, 53, 61, 74, 77, 83, and 84; Violet colored dyes such as C.I. Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; Green dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

The content of the dye is not particularly limited and may be, for example, 0.5 to 80% by weight, preferably 1 to 50% by weight, based on the solid content of the colorant. When the content of the dye is within the above range, it is possible to prevent the problem of lowering the reliability of dye elution by the organic solvent after pattern formation, and the sensitivity is excellent.

The content of the colorant is not particularly limited and may be in the range of 5 to 60% by weight, preferably in the range of 10 to 45% by weight, based on the solid content of the colored photosensitive resin composition. When the content of the colorant is within the above range, the color density of the pixel is sufficient and the non-curing portion of the non-cured portion is not deteriorated during development, so that the occurrence of the residue can be reduced.

<Alkali-soluble resin>

The alkali-soluble resin is not particularly limited as long as it is soluble in the solvent of the present invention and has reactivity to the action of light or heat, functions as a binder resin for the coloring agent and is soluble in an alkaline developing solution Can be used.

Examples of the acrylic copolymer include a copolymer of a carboxyl group-containing monomer and another monomer copolymerizable with the monomer.

Examples of the carboxyl group-containing monomer include unsaturated carboxylic acids such as unsaturated polycarboxylic acids having at least one carboxyl group in the molecule such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or unsaturated tricarboxylic acid. have. These may be used alone or in combination of two or more.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid and the like.

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxy Ethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate and the like. .

Specific examples of other monomers copolymerizable with the carboxyl group-containing monomer include styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o- Styrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, Aromatic vinyl compounds such as benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane having a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain Macromers and the like. These may be used alone or in combination of two or more.

When the alkali-soluble resin is a copolymer of a carboxyl group-containing monomer and another copolymerizable monomer, the content of the carboxyl group-containing monomer is not particularly limited and is, for example, 10 to 50% by weight, preferably 15 to 40% By weight, more preferably 25 to 40% by weight. When the content of the carboxyl group-containing monomer is within the above range, solubility in a developer is good, and an accurate pattern can be formed at the time of development.

Examples of the alkali-soluble resin include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (Meth) acrylate / polymethyl (meth) acrylate copolymer, a (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate macromonomer Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, Acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxy) / styrene (Meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene / (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. Here, (meth) acrylate means acrylate or methacrylate.

Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl / Methyl (meth) acrylate / styrene copolymer and the like are preferable.

The molecular weight of the alkali-soluble resin is not particularly limited and may be, for example, a polystyrene-reduced weight average molecular weight (hereinafter referred to as weight average molecular weight) of 3,000 to 200,000, preferably 5,000 to 100,000. When the molecular weight of the alkali-soluble resin is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed area is good, and the resolution can be improved.

The acid value of the alkali-soluble resin is not particularly limited, and may be, for example, 20 to 200 mg KOH / g, and preferably 30 to 170 mg KOH / g. When the acid value of the alkali-soluble resin is within the above range, the solubility in a developing solution is improved and the residual film ratio can be improved. Acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The content of the alkali-soluble resin is not particularly limited and may be, for example, 10 to 80% by weight, preferably 20 to 70% by weight, based on the solid content of the total amount of the colored photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, a fine pattern can be easily formed, and the resolution and the residual film ratio can be improved.

One embodiment of the method for producing an alkali-soluble resin is as follows.

0.1 to 10% of a polymerization initiator is added to a 0.5 to 20-fold amount of the monomer, monomer, and monomers in the flask having the stirrer, the thermometer, the reflux condenser, the dropping funnel and the nitrogen- . Thereafter, the mixture is stirred at 40 to 140 DEG C for 1 to 10 hours.

As the solvent, those used in the conventional radical polymerization can be used. Specific examples of the solvent include tetrahydrofuran, dioxane, ethyleneglycol dimethylethyl, diethyleneglycol dimethylethyl, acetone, methylethylketone, methylisobutylketone, cyclohexanone Propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, methylene chloride, ethyl acetate, butyl acetate, propyleneglycol monomethyl ethyl acetate, 3-methoxybutyl acetate, Chloroform, dimethylsulfoxide, and the like, or a mixture thereof.

The polymerization initiator may be a polymerization initiator commonly used in the art and is not particularly limited. Specific examples thereof include diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, Organic peroxides such as 2-ethylhexanoate; Azo compounds such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylbarenonitrile) and dimethyl 2,2'-azobis (2-methylpropionate) Nitrogen compounds and the like. These may be used alone or in combination of two or more.

In the above process, an alpha -methylstyrene dimer or a mercapto compound may be used as a chain transfer agent to control the molecular weight. The? -methylstyrene dimer or the mercapto compound may be used in an amount of 0.005 to 5 parts by weight based on 100 parts by weight of the monomer. The above-mentioned polymerization conditions may be appropriately adjusted depending on the production equipment or the amount of heat generated by polymerization and the like.

< Photopolymerization  Compound &gt;

The photopolymerizable compound is a component for enhancing the strength of the pattern, and may include 1 to 6 functional monomers. For example, monofunctional compounds such as nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N- Monomer; (Meth) acrylates such as 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di 3-methylpentanediol di (meth) acrylate, 3- (acryloyloxy) -2-hydroxypropyl methacrylate, 2-hydroxy-1,3-dimethacryloxypropane, Bifunctional monomers such as 2-hydroxy-1-acryloxy-3-methacryloxypropane; Trifunctional monomers such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate; Pentafunctional monomers such as dipentaerythritol penta (meth) acrylate; And hexafunctional monomers such as dipentaerythritol hexa (meth) acrylate. These may be used alone or in combination of two or more.

The photopolymerizable compound may preferably be a bifunctional or higher functional monomer and, more preferably, a pentafunctional or higher functional monomer in view of enhancement of pattern strength and improvement in smoothness.

Examples of commercially available photopolymerizable compounds include 701 (NK ESTER), 701A (NK ESTER), ATMM-3L (NK ESTER) and KAYARAD DPHA (Nippon Kayaku).

The content of the photopolymerizable compound is not particularly limited within a range that the sum of the hydroxyl groups of the alkali-soluble resin and the alkali-soluble resin falls within the above range. For example, the content of the photopolymerizable compound may be in the range of 5 to 50 wt% By weight, preferably 7 to 45% by weight. When the content of the photopolymerizable compound is within the above range, the strength and smoothness of the pixel portion can be good.

< Light curing Initiator >

The photopolymerization initiator according to the present invention includes a compound represented by the following formula (1): &lt; EMI ID =

[Chemical Formula 1]

When the photopolymerization initiator represented by the general formula (1) is included, it is possible to realize high resolution because of improved brightness and excellent sensitivity.

The colored photosensitive resin composition of the present invention may further contain, in addition to the photopolymerization initiator represented by the general formula (1), at least one photopolymerization initiator commonly used in the art within the scope of the present invention. For example, acetophenone, benzoin, benzophenone, triazine, oxime, biimidazole, and thioxanthone compounds. These may be used alone or in combination of two or more.

The acetophenone compound is not particularly limited and includes, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2- hydroxyethoxy) Hexyl phenyl ketone, and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

The benzoin compound is not particularly limited, and examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

The benzophenone compound is not particularly limited, and examples thereof include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- methyldiphenylsulfide, 3,3 ' -Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

The triazine compound is not particularly limited, and examples thereof include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2 , 2,4-bis (trichloromethyl) -6- [2- (5-methylpiperazin-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The oxime compound is not particularly limited, and examples thereof include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -Butane-1,2-butane-2-oxime-O-acetate, 1- (4-methylsulfanyl- Phenyl-phenyl) -acetic acid ethyl ester-O-acetate, and hydroxyimino- (4-methylsulfanyl-phenyl) -acetic acid ethyl ester-O-benzoate.

The imidazole-based compound is not particularly limited, and examples thereof 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' Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2- Phenyl) -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 with a carboalkoxy group , And preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4,5,5'-tetraphenyl- Imidazole and the like.

The thioxanthone compound is not particularly limited, and examples thereof include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Tone and the like.

The content of the photopolymerization initiator is not particularly limited and may be, for example, 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the solid content of the total amount of the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, the colored photosensitive resin composition becomes highly sensitive and the exposure time is shortened, so that productivity is improved and high resolution can be maintained, and the strength of the formed pixel portion and the smoothness on the surface of the pixel portion can be improved have.

The content of the compound represented by the general formula (1) in the photopolymerization initiator is not particularly limited and may be, for example, 10 to 100% by weight, preferably 20 to 100% by weight, based on the total weight of the photopolymerization initiator. When the content of the compound represented by the general formula (1) is within the above range, the luminance and sensitivity can be improved and the effect of realizing a high resolution can be maximized.

< Light curing  Initiation supplements>

The colored photosensitive resin composition of the present invention may further include a photopolymerization initiation auxiliary agent for improving the sensitivity.

The photopolymerization initiator is not particularly limited, and examples thereof include an amine compound, an alkoxyanthracene compound, and a thioxanthone compound. These may be used alone or in combination of two or more.

The amine compound is not particularly limited, and examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.

The alkoxyanthracene compound is not particularly limited and may be, for example, an anthracene compound having an alkoxy group having 1 to 10 carbon atoms, and more specifically, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxy Anthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

The thioxanthone compound is not particularly limited and includes, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4- Chloro-4-propoxyoctanoate and the like.

Examples of commercially available photopolymerization initiation assistants include EAB-F (Hodogaya Chemical Industries, Ltd.).

Examples of the combination of the photopolymerization initiator and the photopolymerization initiator that are preferred for the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan- Phenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) benzophenone,

Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one / 4,4'-bis (diethylamino) benzophenone, And combinations of dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, Morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone.

The content of the photopolymerization initiator is not particularly limited and may be, for example, 10 moles or less, preferably 0.01 to 5 moles, per mole of the photopolymerization initiator. When the content of the photopolymerization initiator is within the above range, the sensitivity of the colored photosensitive resin composition is further improved, and productivity to be formed therefrom can be improved.

<Antioxidant>

The antioxidant according to the present invention comprises a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:

(2)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Or a straight or branched chain alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms)

(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom or An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or a linear or branched alkyl group having 1 to 10 carbon atoms).

The compounds represented by the general formulas (2) and (3) can realize a high resolution by increasing the taper angle, so that a color filter exhibiting high brightness, high sensitivity and high resolution can be manufactured by using the photopolymerization initiator represented by the general formula (1).

In Formula 2, _one of R ₁ , R ₂ , R ₃ and R ₄ or one of R ₅ , R ₆ , R ₇ and R ₈ may not be a hydrogen atom, preferably R ₁ , R ₂ , R ₃ , One of R ₄ and one of R ₅ , R ₆ , R ₇ and R ₈ may not be a hydrogen atom. In such a case, the effect of high-resolution implementation can be further improved.

In Formula 3, one of R ₂ , R ₃ , R ₄ and R ₅ , R ₆ , R ₇ , and R ₈ And R ₉ , or one of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ may not be a hydrogen atom. In such a case, the effect of high-resolution implementation can be further improved.

The antioxidant according to the present invention may further include antioxidants commonly used in the art in addition to the compounds represented by the formulas (2) and (3), for example, 2-t-butyl phenol, 2,6- Di-sec-butylphenol, 2,4-di-tert-butylphenol, 2-sec- , 2,4-diisopropylphenol, 2-t-octylphenol, 2,6-di-t-octylphenol, 2,4-di- Phenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2-t-butyl-p-cresol, 2,6- Butyl-o-cresol, 2,6-di-t-dodecylphenol, 2,4-di-t-dodecylphenol, 2-sec- Octylphenol, 2,4-di-t-octylphenol, 6-sec-butyl-o-cresol, 2- octyl-o-cresol, 6-t-dodecyl-o-cresol, octadecyl-3- (3,5- Di-t-butyl-4- (3-methyl-6-t-butylphenol), triethyleneglycol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [ (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6- (4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-ethylphenol, 2,2'- (3,5-di-tert-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene, tetrakis [methylene- t-butyl-4'-hydroxyphenylpropionate)] methane.

The content of the antioxidant is not particularly limited and may be 1 to 80 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the photopolymerization initiator based on the solid content. When the content of the antioxidant is within the above range, the resolution improving effect can be maximized.

<Solvent>

The solvent is not particularly limited as long as it can dissolve the above components, and examples thereof include ethers, aromatic hydrocarbons, ketones, alcohols, esters and amides. These may be used alone or in combination of two or more.

Examples of the ethers include tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol methyl ether, diethylene glycol monoethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, Ethoxybutylacetate , Methoxy pentyl acetate, anisole, phenetole, methyl anisole, and the like.

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

Examples of the ketone include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone and cyclohexanone .

The alcohols include, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin and the like.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, Methyl lactate, methyl lactate, methyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, , Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropyl Methyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, .

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide and the like. Examples of the other solvent include N-methylpyrrolidone or dimethylsulfoxide and the like. .

The solvent may preferably be ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether, etc., from the viewpoint of coatability and dryness.

The content of the solvent is not particularly limited and includes, for example, a solvent contained in the colorant dispersion. The total amount of the solvent may be 10 to 90% by weight of the total weight of the colored photosensitive resin composition, preferably 20 to 80% %. &Lt; / RTI &gt; When the content of the solvent is within the above range, the coating property may be good.

<Additives>

The colored photosensitive resin composition of the present invention may further contain at least one additive selected from the group consisting of a dispersant, another polymer compound, a curing agent, a surfactant, an adhesion promoter, an ultraviolet absorber and an anti-

The dispersant is added for maintaining deagglomeration and stability of the pigment, and any of those generally used in the art can be used without limitation. Preferably an acrylate-based dispersant comprising BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate); Polycarboxylic acid esters; Unsaturated polyamides; Polycarboxylic acids; (Partial) amine salts of polycarboxylic acids; Ammonium salts of polycarboxylic acids; Alkylamine salts of polycarboxylic acids; Polysiloxanes; Long chain polyaminoamide phosphate salts; Esters of hydroxyl group-containing polycarboxylic acids and their modification products; An amide formed by the reaction of a polyester having a free carboxyl group with a poly (lower alkyleneimine) or a salt 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; Phosphate esters and the like. These may be used alone or in combination of two or more.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK- DISPER BYK-182, DISPER BYK-184, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 (BYK KEMISA); EFKA-44, EFKA-44, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA- 4400, EFKA-4406, EFKA-4510, EFKA-4800 (BASF); SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 (Lubirzol); Hinoact T-6000, Hinoact T-7000, Hinoact T-8000 (Kawaken Fine Chemicals); AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 (Ajinomoto); FLORENE DOPA-17HF, Florene DOPA-15BHF, Florene DOPA-33 and Florene DOPA-44 (Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The other polymer compound is not particularly limited, and examples thereof include curable resins such as epoxy resin and maleimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, Thermoplastic resins and the like.

The curing agent is a component for increasing deep curing and mechanical strength, and the type thereof is not particularly limited, and examples thereof include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, and oxetane compounds.

The epoxy compound is not particularly limited and includes, for example, 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, Epoxy resins, glycidyl ester resins, glycidyl amine resins, or brominated derivatives of such epoxy resins; Aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and brominated derivatives thereof; Butadiene (co) polymeric epoxide; Isoprene (co) polymeric epoxide; Glycidyl (meth) acrylate (co) polymers; Triglycidyl isocyanurate and the like.

The oxetane compound is not particularly limited and includes, for example, carbonate 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 auxiliary compound is not particularly limited, and examples thereof include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators. Commercially available polyvalent carboxylic acid anhydrides can be used as an epoxy resin curing agent.

The commercially available epoxy resin curing agent that can be used in the present invention is not particularly limited and includes, for example, a trade name (Adeka Hadona EH-700) (manufactured by Adeka Kogyo Co., Ltd.), a trade name (Rikashido HH) Ltd.) and a trade name (MH-700) (manufactured by Shin-Etsu Chemical Co., Ltd.).

The surfactant is a component for improving the film-forming property of the photosensitive resin composition, and the kind thereof is not particularly limited, and examples thereof include a fluorine surfactant, a silicone surfactant, or a mixture thereof.

The silicone surfactant is not particularly limited, and examples thereof include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 of Dow Corning Toray Silicone Co., Ltd.; TS F-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 of GE Toshiba Silicones.

Examples of the fluorochemical surfactant include, but are not limited to, Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Examples of the adhesion promoter include, but are not limited to, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl (meth) acrylate, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The content of the adhesion promoter is not particularly limited and may be, for example, 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the colored photosensitive resin composition based on the solid content.

The type of ultraviolet absorber is not particularly limited, and examples thereof include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

The anti-aggregation agent is not particularly limited and may be, for example, sodium polyacrylate.

&Lt; Method for producing colored photosensitive resin composition >

Examples of the method for preparing the colored photosensitive resin composition of the present invention include a method in which a colorant and a dispersant are added to and dispersed in a solvent to prepare a colorant dispersion having a uniform particle diameter and then an alkali soluble resin dissolved in a solvent, A photopolymerization initiator and, if necessary, other additives, etc. are mixed and mixed with the dispersion of the colorant and, if necessary, the solvent is added again.

<Color filter>

The present invention also provides a color filter made of the colored photosensitive resin composition.

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

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

The color layer may be a layer containing the colored photosensitive resin composition of the present invention, and may be a layer formed by applying the colored photosensitive resin composition and exposing, developing, and thermosetting the colored photosensitive resin composition in a predetermined pattern.

The color filter including the substrate and the color layer as described above may further include a partition wall formed between each color pattern, and may further include a black matrix. Further, it may further comprise a protective film formed on the color layer of the color filter.

<Liquid Crystal Display Device>

The present invention also relates to a liquid crystal display device provided with the color filter.

The liquid crystal display device of the present invention may include a configuration known to those skilled in the art without the color filter, and is not particularly limited in the present invention.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  One

As a coloring agent, C.I. 3.43 parts by weight Pigment Red 254, and C.I. 2.81 parts by weight Pigment Red 177; A copolymer of methacrylic acid and benzyl methacrylate as an alkali-soluble resin (ratio of methacrylic acid unit to benzyl methacrylate unit: 20:80, acid value: 83 mgKOH / g, weight average molecular weight in terms of polystyrene: 13,000) 3.95 parts by weight; 1.78 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.8 part by weight of a compound represented by the general formula (1) as a photopolymerization initiator; 0.29 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.09 part by weight of 4,4'-butyidenebis (6-tetra-butyl-3-methylphenol) (BBM-S, Sumitomo Chemical Co., Ltd.) as an antioxidant; 84 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 2.7 parts by weight of a pigment dispersant (BYK-2000, manufactured by BYK) as an additive, 0.02 part by weight of SH8400 by Dow Corning Toray Silicone Co., Ltd. and 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

[Chemical Formula 1]

Example  2

As a coloring agent, C.I. 3.45 parts by weight Pigment Green 58, and C.I. Pigment Yellow 138 1.51 parts by weight; A copolymer of methacrylic acid and benzyl methacrylate as the alkali-soluble resin (the ratio of the methacrylic acid unit to the benzyl methacrylate unit to the methyl (meth) acrylate unit was 32: 50: 18, the acid value was 100 mgKOH / g, weight average molecular weight in terms of polystyrene: 15,000) 2.72 parts by weight; 6.34 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.63 part by weight of a compound represented by the general formula (1) as a photopolymerization initiator; 0.09 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.03 parts by weight of 4,4'-butyidenebis (6-tetra-butyl-3-methylphenol) (BBM-S, Sumitomo Chemical Co., Ltd.) as an antioxidant; 84.01 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 1.09 parts by weight of a pigment dispersant (BYK-2000, BYK) as an additive, 0.02 part by weight of SH8400 of Dow Corning Toray Silicone Co., Ltd. and 0.11 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition Respectively.

Example  3

As a coloring agent, C.I. 2.9 parts by weight of Pigment Blue 15: 6 and 0.27 parts by weight of Rhodamine B (Daoka Chemical Co.); A copolymer of methacrylic acid and benzyl methacrylate as the alkali-soluble resin (the ratio of methacrylic acid unit, benzyl methacrylate unit and styrene unit was 30: 60: 10 in molar ratio, acid value was 90, weight average molecular weight in terms of polystyrene &Lt; / RTI &gt;10,000); 0.86 part by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Powder) as a photopolymerizable compound; 0.86 part by weight of a compound represented by the formula (1) as a photopolymerization initiator; 0.48 part by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.03 parts by weight of 4,4'-butyrylidene bis (6-tetra-butyl-3-methylphenol) (Sumitomo Chemical-BBM-S) as an antioxidant; 88.9 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 0.75 parts by weight of a pigment dispersant (BYK-2000, BYK) as an additive, 0.02 parts by weight of SH8400 of Dow Corning Toray Silicone Co., Ltd. and 0.15 part by weight of methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition And

Example  4

As a coloring agent, C.I. 3.43 parts by weight Pigment Red 254, and C.I. 2.81 parts by weight Pigment Red 177; A copolymer of methacrylic acid and benzyl methacrylate as an alkali-soluble resin (ratio of methacrylic acid unit to benzyl methacrylate unit: 20:80, acid value: 83 mgKOH / g, weight average molecular weight in terms of polystyrene: 13,000) 3.95 parts by weight; 1.78 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.8 part by weight of a compound represented by the general formula (1) as a photopolymerization initiator; 0.29 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.09 parts by weight as an antioxidant (Sumilizer GP, Sumitomo Chemical Co., Ltd.); 84 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 2.7 parts by weight of a pigment dispersant (BYK-2000, manufactured by BYK) as an additive, 0.02 part by weight of SH8400 by Dow Corning Toray Silicone Co., Ltd. and 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

Comparative Example  One

As a coloring agent, C.I. 3.43 parts by weight Pigment Red 254, and C.I. 2.81 parts by weight Pigment Red 177; A copolymer of methacrylic acid and benzyl methacrylate as an alkali-soluble resin (ratio of methacrylic acid unit to benzyl methacrylate unit: 20:80, acid value: 83 mgKOH / g, weight average molecular weight in terms of polystyrene: 13,000) 3.95 parts by weight; 1.78 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.8 part by weight of a compound represented by the general formula (1) as a photopolymerization initiator; 0.29 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 84.09 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 2.7 parts by weight of pigment dispersant (polyester type, polyacrylic type) as an additive, 0.02 part by weight of SH8400 of Dow Corning Toray Silicone Co., Ltd. and 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

Comparative Example  2

As a coloring agent, C.I. 3.45 parts by weight Pigment Green 58, and C.I. Pigment Yellow 138 1.51 parts by weight; A copolymer of methacrylic acid and benzyl methacrylate as the alkali-soluble resin (ratio of methacrylic acid unit, benzyl methacrylate unit and methyl (meth) acrylate unit) of 32:50:18, acid value of 100 mgKOH / g, weight average molecular weight in terms of polystyrene: 15,000) 2.72 parts by weight; 6.34 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.63 part by weight of a compound represented by the general formula (1) as a photopolymerization initiator; 0.09 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.03 parts by weight of AO-503 (Adeka) as an antioxidant; 84.01 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 1.09 parts by weight of a pigment dispersant (polyester type, polyacrylic type) as an additive, 0.02 part by weight of SH8400 from Dow Corning Toray Silicone Co., Ltd. and 0.11 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

Comparative Example  3

As a coloring agent, C.I. 3.43 parts by weight Pigment Red 254, and C.I. 2.81 parts by weight Pigment Red 177; A copolymer of methacrylic acid and benzyl methacrylate as an alkali-soluble resin (ratio of methacrylic acid unit to benzyl methacrylate unit: 20:80, acid value: 83 mgKOH / g, weight average molecular weight in terms of polystyrene: 13,000) 3.95 parts by weight; 1.78 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.8 parts by weight of Irgacure OXE-01 (ciba) as a photopolymerization initiator; 0.29 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.09 parts by weight of 4,4'-butyidenebis (6-tetra-butyl-3-methylphenol) (BBM-S, Sumitomo Chemical Co., Ltd.) as an antioxidant; 84 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 2.7 parts by weight of pigment dispersant (polyester type, polyacrylic type) as an additive, 0.02 part by weight of SH8400 of Dow Corning Toray Silicone Co., Ltd. and 0.13 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

Comparative Example  4

3.45 parts by weight of CI Pigment Green 58 as a coloring agent and 1.51 parts by weight of CI Pigment Yellow 138; A copolymer of methacrylic acid and benzyl methacrylate as the alkali-soluble resin (ratio of methacrylic acid unit, benzyl methacrylate unit and methyl (meth) acrylate unit) of 32:50:18, acid value of 100 mgKOH / g, weight average molecular weight in terms of polystyrene: 15,000) 2.72 parts by weight; 6.34 parts by weight of dipentaerythritol hexaacrylate (DPHA, Japan Chemical Company) as a photopolymerizable compound; 0.63 part by weight of Irgacure OXE-01 (ciba) as a photopolymerization initiator; 0.09 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator; 0.03 parts by weight of AO-503 (Adeka) as an antioxidant; 84.01 parts by weight of propylene glycol monomethyl ether acetate as a solvent; 1.09 parts by weight of a pigment dispersant (polyester type, polyacrylic type) as an additive, 0.02 part by weight of SH8400 by Dow Corning Toray Silicone Co., Ltd. and 0.11 part by weight of 3-methacryloxypropyltrimethoxysilane were mixed and dispersed to prepare a colored photosensitive resin composition .

Experimental Example

The colored photosensitive resin composition solutions prepared in Examples and Comparative Examples were each coated on a glass substrate by a spin coating method and 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 line / space pattern of 1 μm to 50 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 100 μm from the test photomask. At this time, the ultraviolet light source was irradiated at a light intensity of 50 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed and developed in a KOH aqueous solution of pH 10.5 for 1 minute. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a 220 ° C heating oven for 1 hour to prepare a color filter. The film thickness of the color filter prepared above was 2.0 탆.

(1) Luminance ( Color characteristics ) evaluation

The luminance was measured by OSP-SP200 (Olympus) for the RY (luminance) color characteristic value at the color coordinates Rx = 0.645, Gy = 0.554 and By = 0.098. The measurement results are shown in Table 1 below.

(2) pattern Taper angle

The evaluation was made as "O" when the taper angle of a 35 μm pattern formed using a test photomask having a line / space pattern of 1 μm to 50 μm was 40 ° or more, and "×" when the taper angle was 40 ° or less , And the evaluation results are shown in Table 1 below.

(3) Evaluation of resolution

A test pattern having a line / space pattern of 1 to 50 mu m was evaluated as &quot;? &Quot; when 35 mu m pattern formation was possible and 35 mu m pattern formation was impossible, Respectively.

division Luminance Taper angle (°) resolution Example 1 19.51 ○ ○ Example 2 65.82 ○ ○ Example 3 11.72 ○ ○ Example 4 19.52 ○ ○ Comparative Example 1 19.51 X X Comparative Example 2 65.81 X X Comparative Example 3 19.36 X X Comparative Example 4 65.65 X X

Referring to Table 1, it can be confirmed that the color filters manufactured from the colored photosensitive resin compositions of Examples 1 to 4 exhibit excellent overall performances such as brightness, taper angle, and resolution.

However, the color filter made of the composition of the comparative example has a low taper angle and can not realize a high resolution.

Claims (8)

A colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an antioxidant and a solvent;
Wherein said photopolymerization initiator comprises a compound represented by the following general formula (1);
Wherein the antioxidant is a colored photosensitive resin composition comprising a compound represented by the following formula (2), a compound represented by the following formula (3), or a mixture thereof:
[Chemical Formula 1]

(2)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, A linear or branched alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with a cycloalkyl group or an aryl group having 6 to 20 carbon atoms)
(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ independently represent a hydrogen atom or A straight or branched chain alkyl group having 1 to 10 carbon atoms which is substituted or unsubstituted with an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms).
The colored photosensitive resin composition according to claim 1, wherein the acid value of the alkali-soluble resin is 20 to 200 mgKOH / g.
The method according to claim 1, further comprising at least one photopolymerization initiator selected from the group consisting of acetophenone, benzoin, benzophenone, triazine, oxime, biimidazole, Sensitive resin composition.
The colored photosensitive resin composition according to claim 1, wherein the compound represented by Formula 1 is contained in an amount of 10 to 100% by weight based on the total weight of the photopolymerization initiator.
[Claim 3] The process according to claim 1, wherein 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4- Phenol, 2,4-di-sec-butylphenol, 2-isopropylphenol, 2,6-diisopropylphenol, 2,4-diisopropylphenol, 2- octylphenol, 2,4-di-t-octylphenol, 2-cyclopentylphenol, 2,6-dicyclopentylphenol, 2,4-dicyclopentylphenol, 2- , 2,6-di-t-amylphenol, 2,4-di-t-amylphenol, 6-t- Butyl-p-cresol, 2,6-di-t-octylphenol, 2,4-di-t-octylphenol, 6-sec- 2-t-butyl-6-isopropylphenol, 6-t-octyl-o-cresol, 6- dodecyl-o-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'- butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritoltetrakis [3- (3,5 Di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5- Benzene, 2,6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl- T-butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'- -Hydroxyphenylpropionate)] methane. The colored photosensitive resin composition according to claim 1, wherein the antioxidant is at least one selected from the group consisting of:
2. The colored photosensitive resin composition according to claim 1, wherein the total weight of the colored photosensitive resin composition
Wherein the colorant comprises 5 to 60% by weight,
The alkali-soluble resin preferably contains 10 to 80 wt%
The photopolymerizable compound is contained in an amount of 5 to 50% by weight,
The photopolymerization initiator is contained in an amount of 0.1 to 30% by weight;
The antioxidant is contained in an amount of 1 to 80 parts by weight based on 100 parts by weight of the photopolymerization initiator;
Wherein the solvent comprises 10 to 90% by weight of the total weight of the colored photosensitive resin composition.
The colored photosensitive resin composition according to claim 1, further comprising at least one photopolymerization initiation auxiliary selected from the group consisting of an amine compound, an alkoxyanthracene compound and a thioxanthone compound.
A color filter made of the colored photosensitive resin composition according to any one of claims 1 to 7.