KR20160111759A - A color photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition, and a color filter and a display device comprising the same and, more specifically, to a colored photosensitive resin composition having excellent developing rate, sensitivity, and solvent resistance, a color filter and a display device comprising the same. The colored photosensitive resin composition comprises: an alkali soluble resin; a compound including one or more carboxyl groups in molecules and five or more photo-curable vinyl groups; a photopolymerizable compound including a compound including seven or more photo-curable vinyl groups in molecules; a photopolymerizable initiator; and a solvent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photosensitive resin composition, a color filter and a display device using the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter and a display device including the colored photosensitive resin composition, and more particularly to a colored photosensitive resin composition which exhibits excellent development speed, sensitivity and solvent resistance, including a colorant, an alkali-soluble resin, a photopolymerizable compound, To a color filter and a display device including the same.

A color filter used in a liquid crystal display device is formed by forming fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like.

Recently, a method of producing a color filter for a liquid crystal display has been widely used, in which a pigment dispersion method having high productivity and excellent in fine workability, that is, a method using a colored photosensitive resin composition in which a pigment is dispersed is widely used. In this method, a colored photosensitive resin composition in which a pigment is dispersed is applied to a transparent substrate such as glass to form a coated film, and the coated film is exposed to radiation through a photomask, and then the unexposed portion is removed Thereby forming a pattern. Hereinafter, the colored photosensitive resin composition in which the pigment used for producing the color filter is dispersed as described above is referred to as a photosensitive resin composition for a color filter.

The photosensitive resin composition for a color filter usually contains a pigment, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and a surfactant, an adhesion promoter, a residue reducing compound and the like are added thereto.

In recent years, color filters have become increasingly colored with high color rendering and high color reproducibility, and the pigment concentration in the photosensitive resin composition for a color filter has been increasing.

However, when a pixel is formed using a colored photosensitive resin composition having a high content of a coloring material, a developing residue is formed on the substrate of the unexposed portion in the developing process, or the unexposed portion is developed in a separation type, Or the remaining impurities do not dissolve in the process adhere to the pixel and non-pixel portion substrates. In addition, the sensitivity of a pixel formed in the exposed portion is not sufficient, so that the surface of the coating film is defective or the degree of curing is insufficient.

Accordingly, as a method for producing a colored photosensitive resin composition for increasing the sensitivity of a pixel, a technique for improving sensitivity using a photo-curable monomer containing a polyfunctional group as a photopolymerizable compound has been developed, -0030084 discloses a colored photosensitive resin composition using a photo-curable monomer containing a polyfunctional group.

However, recently, the demand for shortening the process time has been increased, but the photocurable monomer containing the multifunctional group has not exhibited a development speed to shorten the processing time. Therefore, when the process time is shortened, there is a problem that a large amount of development residues remain in the resin without being removed during development.

Therefore, even if the process time is shortened, it is necessary to study the photopolymerizable compound which can reduce the development residue and increase the sensitivity.

Korean Patent Publication No. 10-2011-0030084

The present invention relates to a photopolymerizable compound, which uses a compound containing at least one carboxyl group and at least five photocurable vinyl groups in a molecule and a compound containing at least 7 photocurable vinyl groups in the molecule, And is excellent in sensitivity, reliability, and solvent resistance.

It is another object of the present invention to provide a color filter having excellent color reproducibility and a display device including the color filter by using the colored photosensitive resin composition for producing a color filter.

In order to achieve the above object,

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The photopolymerizable compound provides a colored photosensitive resin composition comprising a compound containing at least one carboxyl group and at least five photocurable vinyl groups in a molecule and a compound containing at least 7 photocurable vinyl groups in the molecule.

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

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

The colored photosensitive resin composition of the present invention is a photopolymerizable compound which is obtained by using a compound containing at least one carboxyl group and at least five photocurable vinyl groups in a molecule and a compound containing at least 7 photocurable vinyl groups in the molecule, And is free from development residue, and is excellent in sensitivity, reliability, and solvent resistance.

Further, a color filter having excellent color reproducibility with high color reproducibility and a display device including the same can be manufactured using the colored photosensitive resin composition of the present invention.

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

The present invention relates to a colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent,

The photopolymerizable compound relates to a colored photosensitive resin composition comprising a compound containing at least one carboxyl group and at least five photocurable vinyl groups in a molecule and a compound containing at least 7 photocurable vinyl groups in the molecule.

That is, the present invention uses a compound containing at least one carboxyl group and at least five photocurable vinyl groups in a molecule and a compound containing at least 7 photocurable vinyl groups in the molecule as a photopolymerizable compound, It is possible to provide a colored photosensitive resin composition which does not generate a residue and is excellent in sensitivity, reliability and solvent resistance.

If only a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule is used as the photopolymerizable compound or only a compound containing at least 7 photocurable vinyl groups in the molecule is used alone, And there is a possibility that the developing speed is lowered and residue is generated.

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

(A) Colorant

In the present invention, the colorant comprises at least one pigment, at least one dye or a mixture thereof, preferably at least one pigment.

( a1 ) Pigment

The pigment may be an organic pigment or an inorganic pigment generally used in the art. The pigment may be subjected to a surface treatment using a pigment treatment, a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of the surface of the pigment with a polymer compound, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with an organic solvent or water, or a treatment for removing ionic impurities by ion exchange or the like.

The organic pigments may be various pigments used in printing ink, ink jet ink, etc. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, A pyranthrone pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an anthraquinone pigment, an anthrone pigment, an anthrone pigment, an indanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, a diketopyrrolopyrrole pigment, And the like.

As the inorganic pigment, metal compounds such as metal oxides and metal complex salts can be used. Specific examples of the inorganic pigments include iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, A black pigment, a titanium black, and an oxide of a metal such as a pigment that mixes red, green, and blue to give a black color, or a composite metal oxide.

Particularly, the organic pigments and inorganic pigments may be specifically classified into pigments in the Society of Dyers and Colourists, and more specifically, those having a color index (CI) number Pigments, but are not limited thereto.

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;

And CI Pigment Black 1 and 7 pigments.

These 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, Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. Pigment Green 58. It is preferable to use at least one kind of pigment selected from the group consisting of Pigment Green 58,

When the pigment is mixed with a dye, the pigment is contained in an amount of 50 to 99% by weight, preferably 30 to 99% by weight based on the total weight of the solid content of the colorant. If the content of the pigment is less than 50% by weight, it is difficult to secure the reliability of the colored photosensitive resin composition, and if it exceeds 99% by weight, the transmittance characteristics of the colored photosensitive resin composition are deteriorated.

The pigment is preferably a pigment dispersion in which the particle diameter of the pigment is uniformly dispersed. Examples of a method for uniformly dispersing the particle diameter of the pigment include a method of dispersing the pigment dispersion (a2) by containing the pigment dispersant (a2), and a method of obtaining a pigment dispersion in which the pigment is uniformly dispersed in the solution have.

( a2 ) Pigment Dispersant

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

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

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

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

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

Also, the pigment dispersant preferably includes an acrylate-based dispersant (hereinafter referred to as an acrylate-based dispersant) containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA). Examples of commercially available acrylate dispersants include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 and DISPER BYK-2150. The acrylate dispersants may be used alone or in combination of two or more. .

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

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

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

The pigment dispersant is included in the pigment in an amount of 5 to 60% by weight, preferably 15 to 50% by weight based on the total weight of the solid content. When the pigment dispersant is contained in an amount of less than 5% by weight, it is difficult to atomize the pigment and problems such as gelation may occur after dispersion. When the pigment dispersant is contained in an amount exceeding 60% by weight, the viscosity may be increased.

( a3 )dyes

The dye can be used without limitation as long as it has solubility in an organic solvent. It is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility in an alkali developing solution, heat resistance and solvent resistance.

Examples of the dye 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, Based acid dyes and their derivatives can also be selected. Preferably, the dye is a compound classified as a dye in the color index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing note (color dyeing).

Specific examples of the dye include C.I. As solvent dyes,

C.I. Solvent Red 8, 45, 49, 89, 111, 122, 125, 130, 132, 146 and 179;

C.I. Solvent Blue 5, 35, 36, 37, 44, 59, 67 and 70;

C.I. Solvent Violet 8, 9, 13, 14, 36, 37, 47 and 49;

C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 and 162;

C.I. Solvent Orange 2, 7, 11, 15, 26 and 56;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35.

Of the above CI solvent dyes, CI Solvent Yellow 14, 16, 21, 56, 79, 93, 151 having excellent solubility in an organic solvent; CI Solvent Red 8, 49, 89, 111, 122, 132, 146, 179; CI Solvent Orange 41, 45, 62; CI Solvent Blue 35, 36, 44, 45, 70; CI Solvent Violet 13 is preferred, and CI Solvent Yellow 21, 79; CI Solvent Red 8, 122, 132; CI Solvent Orange 45, 62 is more preferred.

Also, C.I. As an acid 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, 195, 198, 206, 211, 215, 216 , 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349 , 382, 383, 394, 401, 412, 417, 418, 422 and 426;

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, 243 and 251;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169 and 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 and 340;

C.I. Acid Violet 6B, 7, 9, 17, 19 and 66;

Dyes such as C.I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106 and 109.

CI Acid Yellow 42 in the above CI acid dye; CI Acid Red 92; CI Acid Blue 80, 90; CI Acid Violet 66; CI Acid Green 27 is preferable because of its excellent solubility in an organic solvent.

Further, as a C.I. direct dye,

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 and 250;

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 and 141;

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

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

CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79 and 82

Also, as C.I. modantoic dyes,

CI. Modetto Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62 and 65;

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

C. I. Modanto orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 and 48;

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;

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

Dyes such as C.I. Modatto Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43 and 53.

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

When the dye is used together with the pigment, the content of the dye is in the range of 1 to 50% by weight, preferably 1 to 40% by weight, more preferably 5 to 30% by weight based on the total weight of the solid content of the colorant More preferable. If the content of the dye in the colorant is in the range of 1 to 50% by weight, the problem of lowering the reliability of dye elution by the organic solvent after pattern formation can be prevented, and the sensitivity is increased.

The content of the colorant is in the range of 15 to 80% by weight, preferably 30 to 50% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the colorant is contained in the amount of 15 to 80% by weight, the color filter has sufficient color density to form a pattern having sufficient mechanical strength.

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

(B) an alkali-soluble resin

The alkali-soluble resin is prepared by copolymerizing an ethylenically unsaturated monomer containing a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step for forming a pattern.

Specific examples of the ethylenically unsaturated monomer containing 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; Anhydrides of dicarboxylic acids; mono (meth) acrylates of a polymer containing a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate; And acrylic acid and methacrylic acid are preferable.

Further, a hydroxyl group may be added to the alkali-soluble resin in order to secure further developability.

Examples of the method for imparting the hydroxyl group include (1) a method of copolymerizing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group, (2) a method of producing an ethylenically unsaturated monomer containing a carboxyl group (3) a method of preparing a copolymer containing an ethylenically unsaturated monomer containing a carboxyl group and an ethylenically unsaturated monomer containing a hydroxyl group by further reacting a compound containing a glycidyl group with a glycidyl group, and And a method of reacting the compound with the compound of the present invention.

Specific examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 3-phenoxypropyl (meth) acrylate, N-hydroxyethyl acrylamide and the like. Of these, 2-hydroxyethyl (meth) acrylate is preferable, and the ethylenically unsaturated monomer containing a hydroxyl group Two or more species can be used in combination.

Specific examples of the compound containing the glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, 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, preferred are butyl glycidyl ether, aryl glycidyl ether and methacrylic acid glycidyl ester, and the glycidyl group-containing compound may be at least two kinds Can be used in combination.

The unsaturated monomers copolymerizable with the ethylenic unsaturated monomer having a carboxyl group in the production of the alkali-soluble resin may be aromatic vinyl compounds, N-substituted maleimide compounds, alicyclic (meth) acrylates, hydroxyethyl (meth) Acrylates, aryl (meth) acrylates and unsaturated oxetane compounds, but are not limited thereto.

The aromatic vinyl compound is specifically exemplified by styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- , m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

The N-substituted maleimide compound is specifically exemplified by N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide .

Specific examples of the alicyclic (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Alkyl (meth) acrylates such as butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Dicyclopentanyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate.

Specific examples of the hydroxyethyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-hydroxyethyl acrylamide.

Specific examples of the aryl (meth) acrylates include phenyl (meth) acrylate and benzyl (meth) acrylate.

Specific examples of the unsaturated oxetane compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) ) -4-trifluoromethyloxetane, and the like.

The unsaturated monomers may be used alone or in combination of two or more.

The alkali-soluble resin preferably has an acid value of 30 to 150 mgKOH / g in order to ensure compatibility with the dye and storage stability of the colored photosensitive resin composition. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the colored photosensitive resin composition is slow, and when the acid value exceeds 150 mgKOH / g, the adhesion of the colored photosensitive resin composition to the substrate is decreased, There is a problem that compatibility with dyes occurs and dye in the colored photosensitive resin composition is precipitated or the storage stability is lowered and the viscosity is increased.

The alkali-soluble resin is contained in an amount of 1 to 80% by weight, preferably 10 to 50% by weight, based on the total weight of solid components in the colored photosensitive resin composition.

When the content of the alkali-soluble resin is 1 to 80% by weight, a pattern can be formed and the resolution and the residual film ratio can be improved.

(C) Photopolymerization  compound

The photopolymerizable compound is characterized by comprising a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule and a compound containing at least 7 photocurable vinyl groups in the molecule.

Preferably, the compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule is a compound comprising the following formula (1) or (2), and the compound having at least 7 photocurable vinyl groups in the molecule is represented by the following formula 3. ≪ / RTI >

[Chemical Formula 1]

(2)

(3)

If only a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule is used as the photopolymerizable compound or only a compound containing at least 7 photocurable vinyl groups in the molecule is used alone, And there is a possibility that the developing speed is lowered and residue is generated.

Therefore, by using a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule and a compound containing at least 7 photocurable vinyl groups in the molecule as a photopolymerizable compound, the developing rate is excellent, Can be produced, and a colored photosensitive resin composition excellent in sensitivity, reliability and solvent resistance can be provided.

A compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule in an amount of 10 to 90% by weight based on the total weight of the photopolymerizable compound, wherein the compound containing at least 7 photocurable vinyl groups in the molecule 10 to 90% by weight.

When the content of less than 10% by weight of a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule is insufficient for development, residues are generated in the production of a color filter. When the content exceeds 90% by weight, The pattern is peeled off when the color filter is manufactured.

When the content of the compound containing at least 7 photocurable vinyl groups in the molecule is less than 10% by weight, the degree of curing is insufficient, causing a lack of reliability in the production of color filters, If it is contained in an amount exceeding the weight%, the unexposed portion may not be removed during the developing process.

The photopolymerizable compound is contained in an amount of 0.5 to 60% by weight, preferably 5 to 40% by weight based on the total weight of the solid content of the colored photosensitive resin composition. When the photopolymerizable compound is contained in an amount of less than 0.5% by weight, the sensitivity becomes insufficient. When the photopolymerizable compound is contained in an amount exceeding 60% by weight, a problem of poor developability occurs.

(D) Light curing Initiator

The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C).

In particular, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability and price, the photopolymerization initiator is preferably used in combination with an acetophenone based compound, a benzophenone based compound, a triazine based compound, a nonimidazole based compound, It is preferable to use at least one compound selected from the group consisting of compounds.

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

Specific examples of the benzophenone compound include benzophenone, methyl 0-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) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) Bis (2,6-dichlorophenyl) -4, 5,5'-tetra (trialkoxyphenyl) bimidazole, 2,2- , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and imidazole compounds wherein the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group . Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole and 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Can be used.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one, and OXE-01 and OXE-02 of BASF Corporation are typical examples of commercially available products.

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

In addition to the photopolymerization initiators exemplified above, other photopolymerization initiators may be further used in combination within the scope of not impairing the effects of the present invention.

Other photopolymerization initiators include benzoin compounds, anthracene compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10- Methylmorpholine, triphenone, camphorquinone, methylphenylcloxysilicate and titanocene compounds.

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

Specific examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene and 2-ethyl-9,10-diethoxy Anthracene and the like.

The photopolymerization initiator may further include a photopolymerization initiator (D-1) 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 (D-1), whereby the sensitivity can be further increased and productivity can be improved.

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

As the amine compound, an aromatic amine compound is preferably used. Specific examples thereof include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone : Michler's ketone) and 4,4'-bis (diethylamino) benzophenone.

The carboxylic acid compound is preferably an aromatic heteroacetic acid compound. Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, Dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

The organic sulfur compound having a thiol group is specifically exemplified by 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyl Trimethylolpropane tris (3-mercaptopropionate), pentaerythritoltetrakis (3-hydroxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) (Mercaptobutylate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tetraethylene glycol bis (3-mercaptopropionate ) And the like.

The photopolymerization initiator may be contained in the colored photosensitive resin composition of the present invention in an amount of 0.1 to 30% by weight, preferably 1 to 20% by weight based on the total weight of the solid content.

When the photopolymerization initiator is included in the above range, the color photosensitive resin composition becomes highly sensitive and the exposure time is shortened, so that the productivity is improved and high resolution can be maintained. In addition, the strength of the pixel portion formed using the colored photosensitive resin composition and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is preferable to use the same amount of the photopolymerization initiator as the photopolymerization initiator. When the photopolymerization initiator is used in the above amount, the sensitivity of the colored photosensitive resin composition is further improved, It is possible to improve the productivity of the color filter formed.

(E) Solvent

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

Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

And diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether.

Examples of the acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxybutyl acetate, 3 Methoxy-1-butylacetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, methyl 3-methoxypropionate, propylene glycol methyl ether acetate, 3-methoxy- Butyl acetate, 1,2-propylene glycol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, diethylene glycol monobutyl ether Acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, di Ethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate and propylene carbonate. .

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

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

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

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

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

It is preferable to use an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, and examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate Butyl acetate, ethyl lactate, methyl 3-methoxypropionate, and the like.

The solvent is contained in an amount of 60 to 95% by weight, preferably 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent is contained in the range of 60 to 95% by weight, when the solvent is applied by a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) .

(F) Additive

The additive may be optionally added as needed. For example, the additive may include at least one selected from the group consisting of another polymer compound, a hardener, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber and an anti- have.

Among these additives, it is most preferable to include a surfactant.

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 and polyurethane .

The above-mentioned curing agent is used for enhancing deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers and triglycidyl isocyanurate.

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

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 includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Examples of the commercially available products include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), and MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant can be used for further improving the film formation of the colored photosensitive resin composition, and silicon, fluorine, ester, cationic, anionic, nonionic, amphoteric surfactant and the like can be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 of Dow Corning Toray Silicone Co., Ltd. as commercial products, and TSF-4440, TSF-4300, TSF-4445, TSF- -4460 and TSF-4452.

Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated.

Other commercially available products include KP (Shinetsugaku Kagaku Kogyo Co., Ltd.), POLYFLOW (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by TOKEM PRODUCTS CO., LTD.), MEGAFAC Asoui guard, Surflon (available from Asahi Glass Co., Ltd.), SOLSPERSE (Lubrisol) (available from Dainippon Ink and Chemicals Inc.), Flourad (Sumitomo 3M Co., Ltd.) , EFKA (EFKA Chemical), PB 821 (Ajinomoto), and Disperbyk-series (BYK-chemi).

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

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

The nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

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

The type of the adhesion promoter is not particularly limited and specific examples of the adhesion promoter that can be used include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

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

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

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

The kind of the anti-aggregation agent is not particularly limited, but specific examples that can be used include sodium polyacrylate and the like.

The process for producing the colored photosensitive resin composition of the present invention is as follows.

First, the colorant (A) is mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or the whole of the pigment dispersant (a2) and the alkali-soluble resin (B) may be mixed with the solvent (E) and dissolved or dispersed.

(B), a photopolymerizable compound (C), a photopolymerization initiator (D) and, if necessary, an additive (F) and a solvent (E) are further added to the mixed dispersion to a predetermined concentration, To prepare a colored photosensitive resin composition.

The present invention also provides a color filter made of a colored photosensitive resin composition and a display device having the same.

First, a colored photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid component of a previously formed colored photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coat method or a slit coat method. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. The thus obtained coating film is irradiated with ultraviolet rays through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and to precisely align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method is not particularly limited by a liquid addition method, a dipping method, a spraying method, or the like. Further, the substrate may be inclined at an arbitrary angle at the time of development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound is not particularly limited to an inorganic or organic alkaline compound. Examples of the inorganic alkaline compound include inorganic bases such as sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, Potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate and ammonia.

The organic alkaline compound includes, for example, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine , Monoisopropylamine, diisopropylamine, and ethanolamine.

The inorganic or organic alkaline compound may be used alone or in combination of two or more. The concentration of the alkaline compound in the developer is 0.01 to 10% by weight, preferably 0.03 to 5% by weight based on the total weight of the developer.

As the surfactant in the developer, at least one selected from the group consisting of the nonionic surfactant, the anionic surfactant and the cationic surfactant can be used. The concentration of the surfactant in the developing solution is 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight based on the total weight of the developing solution. After development, the substrate is washed with water, and if necessary baked at 150 to 230 DEG C for 10 to 60 minutes.

Using the colored photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through each of the above steps.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

<Preparation of pigment dispersion composition>

Manufacturing example  One.

13.5 parts by weight of CI Pigment Red 177 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 4 parts by weight of 4-hydroxy- 20 parts by weight were mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion composition M1.

Manufacturing example  2.

, 13.5 parts by weight of CI Pigment Green 7 as a pigment, 5.0 parts by weight of DISPERBYK-2001 (manufactured by BYK) as a pigment dispersant, 61.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 4 parts by weight of 4-hydroxy- Were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion composition M2.

&Lt; Preparation of colored photosensitive resin composition &

Example  1 to 5 and Comparative Example  1-4.

The colored photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared with the compositions shown in Table 1 below.

 (Unit: wt%) division Example Comparative Example One 2 3 4 5 One 2 3 4 The pigment dispersion composition (A) M1 57.45 57.45 57.45 - - 57.45 57.45 57.45 M2 - - - 57.45 57.45 - - - 57.45 The alkali-soluble resin (B) 1.58 The photopolymerizable compound (C) C1 2.13 1.42 0.71 2.13 0.71 - 2.84 - - C2 0.71 1.42 2.13 0.71 2.13 - - 2.84 - C3 2.84 - - 2.84 Light curing
Initiator (D) 0.71 Solvent (E) 37.25 Additive (F) 0.17

Pigment dispersion composition (A): Pigment dispersion composition M1 prepared in Preparation Example 1

                     The pigment-dispersed composition M2 prepared in Preparation Example 2

Alkali-soluble resin (B): copolymer of methacrylic acid and benzyl methacrylate (the molar ratio of methacrylic acid unit to benzyl methacrylate unit was 31:69, acid value was 100 mgKOH / g, and polystyrene reduced weight average molecular weight was 20,000)

The photopolymerizable compound (C)

C1: CBZ-SA (Shin-Nakamura Chemical)

C2: T-PE-A (Koei)

C3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

The above-mentioned C1 is a compound including the above-mentioned formulas (1) and (2)

C2 is a compound including the above-described formula (3)

The above C3 is a compound which does not include all of the formulas (1), (2) and (3).

Photopolymerization initiator (D): Irgacure OXE02 (BASF)

Solvent (E): Propylene glycol monomethyl ether acetate

Additive (F): SH-8400 (Dow Corning)

Experimental Example  One. Developability  evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a glass of 5 x 5 cm, dried, and coated to a thickness of 2.5 μm. Thereafter, the resultant was dried in an oven at 100 ° C for 5 minutes, and the solvent was removed to prepare a color filter before exposure to evaluate developability.

The color filter before the exposure was immersed in the KOH aqueous solution of pH 14 and pH 10 for 1 minute and then taken out of the KOH aqueous solution. The color filter was then immersed in distilled water for 1 minute and then taken out and dried in an oven at 100 ° C for 1 minute to check the surface state of the color filter before exposure Respectively.

The results are shown in Table 2. &lt; tb &gt; &lt; TABLE &gt;

&Lt; Development evaluation standard &

○: no residual surface resin is observed at all

DELTA: Surplus of the surface resin is visually recognized, but slightly visible.

X: Residual surface resin is visually recognized

Experimental Example  2. Sensitivity evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a glass of 5 x 5 cm, dried, and then bar-coated to a thickness of 2.5 탆. Thereafter, the solvent was removed by drying in a 100 ° C oven for 3 minutes, and then the color filter was prepared by exposing the solvent to 300 m in terms of the distance from the photomask to 40 mJ of the 313 nm wavelength of the fusion lamp.

The color filter was immersed in a KOH aqueous solution having a pH of 14 for 3 minutes and then taken out. The color filter was immersed in distilled water for 1 minute and then taken out. The color filter was cured in an oven at 230 deg. C for 20 minutes to measure the pattern line width and tearing degree.

The pattern line width was measured by measuring the difference between the line width (X1) of the pattern and the line width (X2) of the photomask.

Evaluation criteria of pattern peeling were as follows, and the results of pattern line width and pattern peeling were shown in Table 2 below.

<Evaluation Criteria of Pattern Cutting>

○: No pattern peeling,

DELTA: 1 to 3 patterns on the pattern,

×: 4 or more patterns peeled off

Experimental Example  3. Solvent resistance  evaluation

Each of the colored photosensitive resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to a glass of 5 x 5 cm, dried, and then bar-coated to a thickness of 2.5 탆. After drying for 3 minutes in a 100 ° C oven to remove the solvent, the color filter was prepared by exposing the mixture to 300 m in terms of the distance from the photomask to 40 mJ of the 313 nm wavelength of the fusion lamp, and curing in an oven at 230 ° C for 20 minutes.

The color filter was immersed in a NMP solution at room temperature for 30 minutes, washed with ultrapure water and dried on a hot plate heated to 120 DEG C for 2 minutes, and the chromaticity before and after immersion was measured.

The equation used here is expressed by the following equation (1) representing the color change in the three-dimensional colorimeter defined by L *, a *, b *. The smaller the color change value, the more reliable the color filter can be manufactured.

The results are shown in Table 2 below.

[Equation 1]

? Eab * = [(? L *) 2+ (? A *) 2+ (? B *) 2] ^0.5

Developability Pattern line width Pattern peeling Solvent resistance Example 1 ○ +8 ○ 2.4 Example 2 ○ +13 ○ 1.8 Example 3 △ +16 ○ 1.2 Example 4 △ +15 ○ 1.4 Example 5 ○ +7 ○ 2.1 Comparative Example 1 △ +1 △ 4.6 Comparative Example 2 ○ -6 × 6.1 Comparative Example 3 × +18 ○ 1.4 Comparative Example 4 △ -One △ 4.3

In the results of Table 2, the colored photosensitive resin composition of the present invention comprising the compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule and the compound containing at least 7 photocurable vinyl groups in the molecule Examples 1 to 5 were observed to have excellent or good developability, sensitivity and solvent resistance.

However, the colored photosensitive resin compositions of Comparative Examples 1 and 4, which contained only a compound containing at least 7 photocurable vinyl groups in the molecule, showed poor pattern line width and poor solvent resistance, and showed that 7 or more photocurable vinyls Group, the pattern line width was poor and pattern peeling was observed, and the result showed that the sensitivity was poor. Further, the colored photosensitive resin composition of Comparative Example 3, which did not contain a compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule, showed poor developability and solvent resistance.

Therefore, the colored photosensitive resin composition of the present invention comprising a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule as a photopolymerizable compound and a compound containing at least 7 photocurable vinyl groups in the molecule It was found through experiments that no residue remained, and the sensitivity and the solvent resistance were excellent.

Therefore, when a color filter having a high color reproducibility is manufactured by using the colored photosensitive resin composition of the present invention, sensitivity and developability degradation that may occur in manufacturing a color filter can be solved.

Claims (9)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
Wherein the photopolymerizable compound comprises a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule and a compound containing at least 7 photocurable vinyl groups in the molecule. The colored photosensitive resin composition according to claim 1, wherein the compound containing at least one carboxyl group and at least five photocurable vinyl groups in the molecule comprises a compound represented by the following formula (1) or (2).
[Chemical Formula 1]

(2)

The colored photosensitive resin composition according to claim 1, wherein the compound containing at least 7 photocurable vinyl groups in the molecule comprises a compound represented by the following formula (3).
(3)

The photocurable composition of claim 1, further comprising 10 to 90% by weight of a compound containing at least one carboxyl group and at least 5 photocurable vinyl groups in the molecule based on the total weight of the photopolymerizable compound and at least 7 photocurable vinyl groups And 10 to 90% by weight of the compound. The colored photosensitive resin composition of claim 1, wherein the colored photosensitive resin composition comprises 15 to 80% by weight of a colorant, 1 to 80% by weight of an alkali-soluble resin, 0.5 to 60% by weight of a photopolymerizable compound, To 30% by weight based on the total weight of the colored photosensitive resin composition, and 60 to 95% by weight of a solvent based on the total weight of the colored photosensitive resin composition. The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition further comprises an additive. The colored photosensitive resin composition according to claim 6, wherein the additive comprises a surfactant. A color filter comprising the colored photosensitive resin composition of claim 1. A display device comprising the color filter of claim 8.