KR20150028524A - 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. More specifically, the colored photosensitive resin composition includes a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerizable initiator (D), a solvent (E), and an additive (F). The coloring agent (A) includes one or more pigments (a1) and one or more dyes (a2), and the additive (F) includes a compound represented by Chemical Formula 1. Accordingly, the colored photosensitive resin composition can produce a color filter pattern having excellent storage stability and high resolution.

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,

The present invention relates to a colored photosensitive resin composition, a color filter, and a liquid crystal display device having the same.

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 colorant, pigments have been used, but in recent years, attempts have been made to use dyes having high brightness and excellent heat resistance. The use of only a dye as a coloring agent is preferable because it can realize all the excellent characteristics of a dye, but the use of the dye is limited because the compatibility with other components of the composition is worse than that of the pigment and the color change is large at high temperatures.

Thus, a method of using a hybrid type coloring agent using both a pigment and a dye as coloring agents has been attempted, but up to now, the problem in using a coloring agent containing a dye has not been completely solved.

In the case of producing a color filter using a colored photosensitive resin composition containing a dye as a coloring agent, discoloration or color change occurs at a post-process at a high temperature, and when the coloring layer is formed due to lack of compatibility with a material to be used, Occurs. In addition, when a color filter is manufactured, the developing speed is low and the sensitivity is insufficient, so that the pattern formed during the development process by the alkaline developer often peels off. Therefore, development of a colored photosensitive resin composition suitable for a lithographic process which contains a dye as a coloring agent or solves the problem of using a dye alone as a coloring agent is desired.

Korean Patent Laid-Open Publication No. 2012-80123 discloses a colored photosensitive composition, a method of manufacturing a color filter, a color filter, a liquid crystal display, and an organic EL display, but does not provide an alternative to the above problem.

Korea Patent Publication No. 2012-80123

It is an object of the present invention to provide a colored photosensitive resin composition capable of forming a color filter pattern of high resolution and having excellent storage stability.

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

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

1. A colorant comprising (A) an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) (a1) and at least one dye (a2), wherein the additive (F) comprises a compound represented by the following formula (1):

[Chemical Formula 1]

(Wherein among, R ₁ represents a hydrogen atom; or a benzyl group; a halogen atom; a hydroxyl group; an aryl group having 6 to 18 carbon atoms; an alkyl group having 1 to 5 carbon atoms, an alkoxy group or alkoxyalkyl group

R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

2. The colored photosensitive resin composition according to 1 above, wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g.

3. The colored photosensitive resin composition according to 1 above, wherein the photopolymerization initiator (D) comprises an oxime ester compound.

4. The compound according to 1 above, wherein R &_lt; ₁ > is a hydrogen atom; A halogen atom; A hydroxyl group; Methyl group; An ethyl group; Methoxy group; Ethoxy; A phenyl group; Benzyl group; Or -CH ₂ OCH ₃ , and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom; A methyl group or an ethyl group.

5. The compound according to 1 above, wherein the compound represented by Formula 1 is selected from the group consisting of succinimide, N-methylsuccinimide, N-ethylsuccinimide, ethosuccimide, N-hydroxysuccinimide, N- Is at least one selected from the group consisting of succinimide, N-chloro succinimide and N-iodosuccinimide.

6. The colored photosensitive resin composition according to 1 above, wherein the compound represented by Formula 1 is at least one selected from the group consisting of succinimide and N-methylsuccinimide.

7. The composition of claim 1, wherein the compound represented by Formula 1 is contained in an amount of 0.1 to 40% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C). Colored photosensitive resin composition.

8. A color filter formed using the colored photosensitive resin composition according to any one of items 1 to 7 above.

9. A liquid crystal display device provided with the color filter according to the above 8.

By using specific additives, the colored photosensitive resin composition according to the present invention is capable of forming a color filter pattern having a high storage stability and high resolution even when a dye is used as a coloring agent.

The present invention includes a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) (A) and at least one kind of dye (a2), and the additive (F) contains a compound represented by the general formula (1), whereby a colored photosensitive resin composition which is excellent in storage stability and capable of forming a color filter pattern with high resolution .

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

The colored photosensitive resin composition of the present invention comprises a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F).

≪ Colorant (A) >

 The colorant (A) according to the present invention comprises at least one kind of pigment (a1) and at least one kind of dye (a2), and by using the pigment (a1) and the dye (a2) at the same time, And is also excellent in compatibility with other components.

Pigment ( a1 )

The kind of the pigment (a1) is not particularly limited, and organic pigments or inorganic pigments generally used in the art can be used.

The above-mentioned pigments include various pigments used in printing ink, ink-jet ink and the like, and specifically include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments , Anthanthrone pigments, indanthrone pigments, pravanthrone pigments, pyranthrone pigments (for example, pyranthrone pigments, perynone pigments, perynone pigments, perynone pigments, anthraquinone pigments, dianthraquinone pigments, anthrapyrimidine pigments, anthanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like. Specific examples of the inorganic pigment include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxide, carbon black and the like.

Particularly, the organic pigments and inorganic pigments may be compounds classified as pigments in the color index (published by The Society of Dyers and Colourists), and more specific examples thereof include pigments having a color index (CI) But are not limited to these.

C.I. Pigment Yellow 13, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180 And 185;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 208, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58;

C.I. Pigment Brown 28;

C.I. Pigment Black 1 and 7 and the like.

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

The exemplified C.I. Among the pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 122, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 208, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment selected from Pigment Green 58 can be preferably used.

It is preferable to use a pigment dispersion in which the particle diameter of the pigment (a1) is uniformly dispersed. An example of a method for uniformly dispersing the particle diameter of the pigment includes a method of dispersing the pigment dispersion (a3) by containing the pigment dispersant (a3). According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained have.

In the colored photosensitive resin composition of the present invention, the pigment (a1) may be contained in the form of a pigment dispersion composition.

The pigment (a1) may be contained in an amount of 20 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the solid content in the pigment dispersion composition. If the content of the pigment is not within the above range, the viscosity may be high and the storage stability may be deteriorated.

Pigment dispersant ( a3 )

The pigment dispersant (a3) is added to maintain the deaggregation and stability of the pigment, and any of those generally used in the art can be used without limitation. An acrylate-based dispersant (hereinafter also referred to as an " acrylic dispersant ") containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Dispersing BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 and DISPER BYK LPN-6919 are examples of commercially available acrylate dispersants. The acrylic dispersants exemplified above may be used alone or in combination of two or more.

As the pigment dispersant (a3), other resin type pigment dispersants other than the acrylic dispersant may be used.

Examples of the other resin type pigment dispersant (a3) include polycarboxylic acid esters represented by polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, polycarboxylic acids An alkylamine salt of a polycarboxylic acid, a polysiloxane, a long-chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, or a polyester having a free carboxyl group and a poly Amide formed by the reaction of (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, and phosphate esters.

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

The content of the pigment dispersant (a3) is preferably 5 to 60 parts by weight, and more preferably 15 to 50 parts by weight based on 100 parts by weight of the solid content of the pigment (a1). If the content of the dispersant (a3) exceeds 60 parts by weight, the viscosity may be increased. If the content of the dispersant (a3) is less than 5 parts by weight, it may be difficult to atomize the pigment or cause gelation after dispersion.

In addition to the above-mentioned dispersing agents, surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants and the like may be used as a dispersant, and these may be used alone or in combination of two or more.

Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimine (Manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), Megafac (Manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Asahi Glass Co., Ltd.), Mitsubishi Kasei MEGAFAC (manufactured by Dainippon Ink and Chemicals, Inc.), Flourad (manufactured by Sumitomo 3M Limited), Asahi guard, Surflon EFKA (manufactured by EFKA Chemical), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.

dyes( a2 )

The dye can be used without any particular limitation as long as it has solubility in an organic solvent. Preferably, the dye has solubility in an organic solvent and is capable of securing reliability such as solubility in alkali developer, heat resistance, solvent resistance, etc. It is good to do.

Examples of the dyes include acid dyes having an acidic group such as sulfonic acid and carboxylic acid, salts of an acidic dye and a nitrogen-containing compound, sulfonamides of an acidic dye and derivatives thereof, and azo dyes, Phthalocyanine-based acid dyes and derivatives thereof can also be used.

Preferable examples of the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and dyes described in dyeing notes (color dyeing).

Specific examples of the dye include 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, 45, 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.

The exemplified C.I. Solvent dye having excellent solubility in an organic solvent. 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 is preferred, and C.I. Solvent Yellow 21, 79; C.I. Solvent Red 8, 122, 132; C.I. Solvent Orange 45, 62 is more preferred.

Also, C.I. As the acid dye,

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, Yellow dyes such as 1,190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243,

C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 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, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 266, 268, Red dyes such as 382, 383, 394, 401, 412, 417, 418, 422, 426;

C.I. Orange dyes such as Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C.I. Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 1, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 335, and 340;

C.I. Violet dyes such as Acid Violet 6B, 7, 9, 17, 19, 66 and the like;

C.I. Green dyes such as Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106,

In the exemplified acid dyes described above, C.I. Acid Yellow 42; C.I. Acid Red 92; C.I. Acid Blue 80, 90; C.I. Acid Violet 66; C.I. Acid Green 27 is preferred.

C.I. As a direct dye,

C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 136, 138 and 141;

C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C.I. Orange dyes such as Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Direct Blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 164, 166, 167, 170, 171, 172, 173, 188, 189, 169, 169, 160, 161, 162, 163, 164, 248, 242, 243, 244, 245, 247, 248, 228, 229, 238, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275 and 293;

C.I. Violet dyes such as Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104;

C.I. Green dyes such as Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like.

Also, C.I. As modatto dyes,

C.I. Yellow dyes such as Modan Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C.I. Modal Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 , 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

C.I. Orange dyes such as Modanato Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, ;

C.I. 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83 and 84;

C.I. Violet colored dyes such as Modanth violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

C.I. Green dyes such as Modan green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43,

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

The content of the dye in the colorant (A) may be 0.5 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 1 to 50% by weight, based on the solid content in the colorant (A) . When the content of the dye in the colorant (A) is in the above range, it is possible to prevent the problem of lowering the reliability of dye elution by organic solvent after pattern formation, and it is preferable because of excellent sensitivity.

The colorant (A) may be contained in an amount of 5 to 60% by weight, preferably 10 to 45% by weight, based on the solid content in the colored photosensitive resin composition of the present invention. When the colorant (A) is contained in an amount of from 5 to 60% by weight, even if a thin film is formed, the color density of the pixel is sufficient and the residue of the non-curing portion is not deteriorated during development.

In the present invention, the total solid content in the colored photosensitive resin composition means the total content of the remaining components excluding the solvent from the colored photosensitive resin composition.

≪ Alkali-soluble resin (B) >

The alkali-soluble resin (B) according to the present invention can be produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group so as to have solubility in an alkali developing solution used in a development processing step for forming a pattern.

The alkali-soluble resin (B) of the present invention preferably has an acid value of 30 to 150 mgKOH / g in order to ensure compatibility with the dye (a2) and storage stability of the colored photosensitive resin composition of the present invention.

When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 150 mgKOH / g, the adhesion with the substrate is decreased, And there is a problem in compatibility with the dye, so that the dye in the colored photosensitive resin composition precipitates or the storage stability of the colored photosensitive resin composition deteriorates, and the viscosity tends to rise.

Specific examples of the ethylenically unsaturated monomer (b1) having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; And an anhydride of the dicarboxylic acid; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

The ethylenically unsaturated monomer (b1) having a carboxyl group and the ethylenically unsaturated monomer (b2) having a hydroxyl group can be copolymerized with an ethylenically unsaturated monomer (b1) having a carboxyl group in order to impart a hydroxyl group to the alkali-soluble resin (B) (B3) having a glycidyl group in the copolymer of the present invention. (B3) having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.

Specific examples of the glycidyl group-containing compound (b3) include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butyrate, glycidyl methyl But are not limited to, ether, ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, Ethers and methacrylic acid glycidyl esters. Of these, butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester are preferable, and two or more kinds of them can be used in combination.

The unsaturated monomer (b4) which can be copolymerized in the production of the alkali-soluble resin (B) is not particularly limited, and examples thereof include styrene, vinyltoluene,? -Methylstyrene, p- M-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m- Aromatic vinyl compounds such as cy- idyl ether and p-vinylbenzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decan- Alicyclic (meth) acrylates such as chloropentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like.

The above-exemplified monomers (b4) having a copolymerizable unsaturated bond may be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) may be 10 to 80% by weight, preferably 10 to 70% by weight, based on the solid content in the photosensitive resin composition of the present invention. When the content of the alkali-soluble resin (B) is in the range of 10 to 80% by weight, solubility in a developing solution is sufficient, pattern formation is easy, and film reduction of the pixel portion of the exposed portion is prevented during development, It is preferable that the dropout property is improved.

≪ Photopolymerizable compound (C) >

The photopolymerizable compound (C) according to the present invention is a compound which can be polymerized by the action of the photopolymerization initiator (D), and monofunctional monomers, bifunctional monomers or polyfunctional monomers can be used, It is good to use.

The type of the monofunctional monomer is not particularly limited, and examples thereof include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate N-vinylpyrrolidone, and the like.

The type of the bifunctional monomer is not particularly limited and examples thereof include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The type of the polyfunctional monomer is not particularly limited and includes, for example, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (metha) acrylate, propoxylated Dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

The content of the photopolymerizable compound (C) is not particularly limited, but may be 5 to 45 wt%, preferably 7 to 45 wt%, based on the solid content in the colored photosensitive resin composition of the present invention. When the photopolymerizable compound (C) is contained in an amount of 5 to 45% by weight, the strength and smoothness of the pixel portion can be maintained satisfactorily.

≪ Photopolymerization initiator (D) >

The photopolymerization initiator (D) according to the present invention can be used without any particular limitation as long as it can polymerize the photopolymerizable compound (C), and in particular, an acetophenone compound, a benzophenone compound, a triazine compound , A non-imidazole-based compound, a thioxanthone-based compound, and an oxime ester-based compound is preferably used.

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

Specific 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.

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, 2,4 Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole-based compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -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 , Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole .

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone And the like.

Specific examples of the oxime ester compound include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and commercially available products include Irgacure OXE-01 (BASF), Irgacure OXE O2E, N-1919 and NCI-831 are preferred from the viewpoint of curing efficiency.

The photopolymerization initiator (D) may further include a photopolymerization initiator to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention contains a photopolymerization initiation auxiliary agent, whereby the sensitivity can be further increased and the productivity can be improved.

Examples of the photopolymerization initiator include 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.

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, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl dimethylbenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (Diethylamino) benzophenone, and the like, and it is preferable to use an aromatic amine compound.

Concrete examples of the carboxylic acid compound include aromatic heteroacetic acid compounds. Phenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, methylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, 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-mercaptobutyloxy Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3- mercaptopropionate) (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate) And the like.

The photopolymerization initiator (D) may be contained in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the solid content of the colored photosensitive resin composition. When the photopolymerization initiator (D) is contained in an amount of 0.1 to 10% by weight, the colored photosensitive resin composition of the present invention has high sensitivity and shortens the exposure time, which is preferable because productivity can be improved and high resolution can be maintained. In addition, the strength of the pixel portion and the smoothness on the surface of the pixel portion can be improved.

As the photopolymerization initiator (D), it is preferable to use an oxime ester compound. The content of the oxime ester compound is not particularly limited, but may be, for example, 10 to 100% by weight of the total photopolymerization initiator, And preferably 20 to 100% by weight. When the content of the oxime ester compound is less than 10% by weight, the decrease in sensitivity due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process.

When the photopolymerization initiator is used, the content of the photopolymerization initiator is not particularly limited. For example, the content of the photopolymerization initiator may be in the range of 0.1 - To 40% by weight, and preferably 1 to 30% by weight. When the use amount of the photopolymerization initiator is within the range of 0.1 to 40% 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 .

≪ Solvent (E) >

The solvent (E) according to the present invention is used for dissolving other components of the colored photosensitive resin composition of the present invention, and can be used without any particular limitation as long as it is a solvent used in a commonly used colored photosensitive resin composition. , Aromatic hydrocarbons, ketones, alcohols, esters, amides and the like are preferable.

Specific examples of the solvent (E) 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 dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol 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;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl 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;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as? -Butyrolactone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like. The above-exemplified solvents (E) may be used alone or in combination of two or more.

The content of the solvent (E) is not particularly limited and may be, for example, 35 to 90% by weight, preferably 40 to 85% by weight based on the total weight of the colored photosensitive resin composition of the present invention. When the amount of the solvent (E) is in the range of 35 to 90% by weight, the coatability can be improved.

≪ Additive (F) >

The additive (F) according to the present invention includes a compound represented by the following formula (1). When the compound represented by Formula 1 is included, a color filter having excellent storage stability and high resolution can be produced.

[Chemical Formula 1]

In the formula, R ₁ represents a hydrogen atom; A halogen atom; A hydroxyl group; An alkyl group, an alkoxy group or an alkoxyalkyl group having 1 to 5 carbon atoms; An aryl group having 6 to 18 carbon atoms; Or a benzyl group, and R ₂ , R ₃ , R _4, and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Also, in the formula, R ₁ represents a hydrogen atom; A halogen atom; A hydroxyl group; Methyl group; An ethyl group; Methoxy group; Ethoxy; A phenyl group; Benzyl group; Or -CH ₂ OCH ₃ and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom; A methyl group or an ethyl group.

The kind of the compound represented by the formula (1) is not particularly limited and includes, for example, succinimide, N-methylsuccinimide, ethosuccinimide, N- ethylsuccinimide, N- N-bromosuccinimide, N-chlorosuccinimide, N-iodosuccinimide, and the like, preferably, succinimide or N-methylsuccinimide. These may be used alone or in combination of two or more.

The content of the compound represented by the formula (1) is not particularly limited and may be, for example, 0.1 to 40% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) By weight, preferably 1 to 30% by weight. When the compound represented by Formula 1 is contained in an amount of 0.1 to 40% by weight, the color photosensitive resin composition of the present invention can maintain high resolution and improve storage stability without peeling of the pattern. Specifically, when it is less than 0.1% by weight, it is difficult to achieve high resolution and excellent storage stability. If it exceeds 40% by weight, a short circuit of the pattern tends to occur during the development process.

If necessary, the colored photosensitive resin composition of the present invention may contain additives such as fillers, other polymer compounds, curing agents, adhesion promoters, ultraviolet absorbers, flocculants, and inhibitors in addition to the above components.

 The filler may be glass, silica, alumina, or the like, but is not limited thereto.

Specific examples of the other polymer compound include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like But is not limited thereto.

The curing agent is used for increasing the curing depth and mechanical strength. Specifically, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound may be used, but the present invention is not limited thereto.

Specific examples of the epoxy compound 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, triglycidyl isocyanurate, and the like, but are not limited thereto.

Specific examples of the oxetane compound include, but are not limited to, carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane. It is not.

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. Specific examples of the curing auxiliary compound include polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as epoxy resin curing agents. Examples of commercially available epoxy resin curing agents include trade name (ADEKA HARDONA EH-700) (ADEKA INDUSTRIAL CO., LTD.), Trade name (RICACIDO HH) (Manufactured by Shin-Etsu Chemical Co., Ltd.).

The curing agents and curing auxiliary compounds exemplified above 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- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane, or a mixture thereof.

The adhesion promoter may be contained in an amount of preferably 0.01 to 10 parts by weight, more preferably 0.05 to 2 parts by weight, based on the solid content of the composition.

Specific examples of the ultraviolet absorber include, but are not limited to, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

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

≪ Method for producing colored photosensitive resin composition >

As a method for producing the colored photosensitive resin composition of the present invention, for example, the pigment (a1) in the colorant (A) is first mixed with the solvent (E) Bead mill or the like. At this time, the pigment dispersant (a3), part or all of the alkali-soluble resin (B) or the dye (a2) may be mixed and dissolved or dispersed together with the solvent (E). The dye (a2), the remainder of the alkali-soluble resin (B), the photopolymerizable compound (C), the photopolymerization initiator (D) and the additive (F) and, if necessary, the solvent (E) The colored photosensitive resin composition according to the present invention can be prepared.

<Color filter>

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

A color filter according to an embodiment of the present invention includes a colored layer formed by applying the colored photosensitive resin composition of the present invention on a substrate, and exposing, developing, and thermally curing the color filter 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 can be carried out by a method known in the art, including a conventional application step; 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 hydrogen phosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Sodium hydrogencarbonate, potassium hydrogencarbonate, 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, polyoxyethylene alkylamines, and the like. 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 surfactant may be included in the developer in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight.

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.

<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.

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.

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.

Manufacturing example  1: Pigment dispersion composition ( M1 )

C.I. , 13.5 parts by weight of Pigment Green 58, 5.0 parts by weight of BYK LPN-6919 (manufactured by BYK) as a pigment dispersant, and 81.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed and dispersed by a bead mill for 12 hours to obtain a pigment dispersion composition M1 .

Manufacturing example  2: alkali-soluble resin (B)

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was charged with 120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of azobisisobutyronitrile (AIBN) 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 57 parts by weight of p-methylstyrene, 20 parts by weight of methyl methacrylate and 3 parts by weight of n-dodecyl mercapto were charged and replaced with nitrogen. Thereafter, the temperature of the reaction solution was elevated to 110 DEG C with stirring, and the reaction was carried out for 6 hours. The alkali-soluble resin thus synthesized had a solid dispersion value of 100.2 mgKOH / g and a weight average molecular weight Mw of about 15110 as measured by GPC.

Example  1: colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Preparation Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Preparation Example 2, 3.99 weight% of Irgacure OXE-02 (manufactured by BASF), 3.99 weight% of succinimide (Aldrich), and 41.50 weight% of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition Respectively.

Example  2: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Preparation Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Preparation Example 2, 3.99% by weight of N-methylsuccinimide (TCI) and 41.50% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin A composition was prepared.

Comparative Example  1: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Preparation Example 1, 0.52% by weight of Solvent Yellow 21 as a dye, 10.22% by weight of an alkali-soluble resin obtained in Preparation Example 2, (Manufactured by Nippon Kayaku Co., Ltd.), 1.00 wt% of Irgacure OXE-02 (BASF), and 45.49 wt% of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  2: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Production Example 1, 10.22% by weight of the alkali-soluble resin obtained in Production Example 2, 3.40% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., 1.00% by weight of Irgacure OXE-02 (BASF), 3.99% by weight of succinimide (Aldrich) and 42.02% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  3: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Production Example 1, 10.22% by weight of the alkali-soluble resin obtained in Production Example 2, 3.40% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., 1.00% by weight of Irgacure OXE-02 (BASF), 3.99% by weight of N-methylsuccinimide (TCI) and 42.02% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Comparative Example  4: Preparation of colored photosensitive resin composition

39.37% by weight of the pigment dispersion composition (M1) obtained in Production Example 1, 10.22% by weight of the alkali-soluble resin obtained in Production Example 2, 3.40% by weight of dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., 1.00% by weight of Irgacure OXE-02 (BASF) and 45.49% by weight of propylene glycol monomethyl ether acetate were mixed to prepare a colored photosensitive resin composition.

Experimental Example  One

A color filter was prepared using the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples. Specifically, each of the above-mentioned colored photosensitive resin compositions was applied on a 2-inch-square glass substrate ("EAGLE XG" manufactured by Corning Inc.) by spin coating, and then placed on a heating plate and maintained at 100 ° C. for 3 minutes to form a thin film . Then, a test photomask having a line / space pattern of 1 μm to 100 μm was placed on the thin film and irradiated with ultraviolet rays at a distance of 300 μm from the test photomask. At this time, the ultraviolet light source was irradiated at 60 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 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 230 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.4 占 퐉.

Experimental Example  2

Each color filter was prepared in the same manner as in Experimental Example 1 except that the test photomask was not used.

Test Methods

(1) Resolution measurement

The pattern of the color filter prepared in Experimental Example 1 is analyzed by an optical microscope (x1000) and the minimum pattern size that can be formed without loss of pattern is shown in Table 1 below

(2) Development speed measurement

The time taken for the non-visible portion to completely dissolve in the developing solution when the color filter manufactured in Experimental Example 1 was manufactured was measured, and the results are shown in Table 1 below

(3) Evaluation of viscosity change

The initial viscosity of the colored photosensitive resin compositions prepared in the above Examples and Comparative Examples was measured, and after storing for 3 months at 5 ° C, the viscosity was measured to observe the viscosity change. The viscosity was measured with a Brookfield viscometer (Brookfield Viscometer DVI +, manufactured by BROOKFIELD) at 25 ° C. The measurement results are shown in Table 1 below.

○: Viscosity change 5% or less

: Change in viscosity: more than 5% and not more than 10%

×: Viscosity change exceeding 10%

(4) Measurement of transmittance

The color filter prepared in Experimental Example 2 was measured for transmittance in the visible light region using a colorimeter (OSP-200, manufactured by Olympus Corporation).

division Minimal pattern
(탆) Development speed
(second) Viscosity change Transmittance
(%) Example 1 20 17 ○ 57.1 Example 2 25 19 ○ 56.8 Comparative Example 1 80 26 X 57.0 Comparative Example 2 45 16 ○ 55.3 Comparative Example 3 50 17 ○ 55.1 Comparative Example 4 45 28 △ 55.4

As shown in Table 1, the color photosensitive resin composition according to the present invention can produce a color filter with a high resolution because the minimum pattern size that can be formed without pattern loss is remarkably small and the developing speed is fast, And the storage stability was excellent.

Further, by using both the dye and the pigment as the coloring agent, it was confirmed that the pigment had an absorption area wider than that of the comparative examples 2 to 3 using only the pigment, and excellent color characteristics.

In the case of Comparative Example 1 in which no additive was used, it was confirmed that the minimum pattern size was very large and the development speed was very slow as compared with the examples, and the storage stability was lowered due to the viscosity change exceeding 10%.

In the case of Comparative Examples 2 and 3 in which only the pigment was not used but the dye was used, the use of the additive of Chemical Formula 1 resulted in a small change in viscosity and a high development speed. However, the minimum pattern size that can be formed without loss of pattern was large, It did not fit. Also, it was confirmed that the transmittance value was decreased and the color characteristic was lowered than in the Examples.

In the case of Comparative Example 4, it was confirmed that the viscosity of the pigment was not changed due to the absence of the additive of Formula 1, and that the minimum pattern size was large without loss of the pattern. It was confirmed that the transmittance was decreased.

Claims (9)

Wherein the colorant (A) comprises at least one pigment (a1), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E) and an additive (F) ) And at least one dye (a2), wherein the additive (F) comprises a compound represented by the following formula (1):
[Chemical Formula 1]

(Wherein among, R ₁ represents a hydrogen atom; or a benzyl group; a halogen atom; a hydroxyl group; an aryl group having 6 to 18 carbon atoms; an alkyl group having 1 to 5 carbon atoms, an alkoxy group or alkoxyalkyl group
R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) has an acid value of 30 to 150 mgKOH / g.
The colored photosensitive resin composition according to claim 1, wherein the photopolymerization initiator (D) comprises an oxime ester compound.
[2] The compound according to claim 1, wherein R &_lt; ₁ &gt; A halogen atom; A hydroxyl group; Methyl group; An ethyl group; Methoxy group; Ethoxy; A phenyl group; Benzyl group; Or -CH ₂ OCH ₃ , and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom; A methyl group or an ethyl group.
The compound according to claim 1, wherein the compound represented by Formula 1 is selected from the group consisting of succinimide, N-methylsuccinimide, N-ethylsuccinimide, ethosuccimide, N-hydroxysuccinimide, N- Amide, N-chlorosuccinimide, and N-iodosuccinimide.
The colored photosensitive resin composition according to claim 1, wherein the compound represented by Formula 1 is at least one selected from the group consisting of succinimide and N-methylsuccinimide.
[2] The composition of claim 1, wherein the compound represented by Formula 1 is contained in an amount of 0.1 to 40% by weight based on the solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C). Colored photosensitive resin composition.
A color filter formed using the colored photosensitive resin composition according to any one of claims 1 to 7.
A liquid crystal display device comprising the color filter according to claim 8.