TWI670334B - Colored photosensitive resin composition and color filter using the same - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition and a color filter manufactured using the same, and more particularly, to a colored photosensitive resin composition for a color filter used when manufacturing a color filter used in a color liquid crystal display device and the like, and to use the same. Manufactured color filters. It is characterized by excellent adhesiveness and peeling characteristics at the time of manufacturing a color filter using the coloring photosensitive resin composition of this invention.

Description

Colored photosensitive resin composition and color filter using the same

The present invention relates to a colored photosensitive resin composition and a color filter using the same, and more particularly, to a colored photosensitive resin composition for a color filter used when manufacturing a color filter used in a color liquid crystal display device and the like, and to use the same Manufactured color filters.

Color filters are widely used in imaging elements, liquid crystal display devices, and the like, and their application range is rapidly expanding. A color filter used in a color liquid crystal display device, an image pickup element, and the like is generally manufactured by uniformly coating a coloring sensitivity containing a coloring agent corresponding to each of red, green, and cyan by spin coating on a substrate formed with a black matrix pattern. After the resin composition, the coating film formed by heating and drying (hereinafter sometimes referred to as pre-firing) is exposed, developed, and further heat-cured as necessary (hereinafter sometimes referred to as post-firing). This operation is performed for each type. Colors are repeated to form pixels of each color (Korean Published Patent No. 10-1998-0010626).

On the other hand, when manufacturing a color filter from a colored photosensitive resin composition, research in the field of improvement of adhesion and The improvement of peeling characteristics has not been proposed as a coloring photosensitive resin composition that has significantly improved adhesiveness and peeling characteristics compared with the prior art.

Prior art literature Patent literature

Patent Document 1: Korean Published Patent No. 10-1998-0010626

Therefore, an object of the present invention is to provide a coloring photosensitive resin composition having improved adhesion and peeling characteristics compared with the prior art at the time of manufacturing a color filter, and a color filter using the same.

Accordingly, the present invention provides a colored photosensitive resin composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), which are The alkali-soluble resin includes a compound represented by the following Chemical Formula 1 and a compound represented by the following Chemical Formula 2. The alkali-soluble resin has a weight average molecular weight of 25,000 to 32,000, and the alkali-soluble resin has an acid value of 50 to 100 mgKOH / g.

[Chemical Formula 1]

In the above Chemical Formula 1, each R1 is independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

In the above Chemical Formula 2, R2 is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

In one embodiment, the colorant (A) may include one or more green pigments or green dyes.

In another embodiment, the alkali-soluble resin may include a compound represented by the following Chemical Formula 3 and a compound represented by the following Chemical Formula 4.

[Chemical Formula 3]

In another embodiment, based on the total weight of the solid content of the colored photosensitive resin composition, the colorant (A) may be contained in an amount of 5 to 60% by weight, and the alkali-soluble resin (B) may be contained in an amount of 10 to 80% by weight. Containing 5 to 50% by weight of the above photopolymerizable compound (C), based on the total solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C), containing 0.1 to 40% by weight of the above-mentioned photopolymerization initiation The agent (D) contains 60 to 90% by weight of the solvent (E) based on the total weight of the colored photosensitive resin composition.

Moreover, this invention provides the color filter manufactured using the said coloring photosensitive resin composition.

It is characterized by excellent adhesiveness and peeling characteristics at the time of manufacturing a color filter using the coloring photosensitive resin composition of this invention.

FIG. 1 shows the evaluation criteria of the peeling characteristics.

The present invention relates to a colored photosensitive resin composition, and more particularly, to a colored photosensitive resin composition for a color filter used in manufacturing a color filter used in a color liquid crystal display device and the like, and a color filter manufactured using the same.

The present invention is described in detail below.

Colorant (A)

The colorant (A) contains one or more pigments (a1) and one or more dyes (a2) as essential components.

Pigment (a1)

The pigment (a1) may be an organic pigment or an inorganic pigment generally used in this field. As the organic pigment, various pigments used in printing inks, inkjet inks, and the like can be used. Specifically, examples of the organic pigment include a water-soluble azo pigment, an insoluble azo pigment, a phthalocyanine pigment, a quinacridone pigment, an isoindololinone pigment, an isoindolline pigment, a fluorene pigment, a fluorenone pigment, Dioxazine pigments, anthraquinone pigments, bi-anthraquinone pigments, anthrapyrimidine pigments, anthhanone pigments, indanthrone pigments, xanthones pigments, pyranthrone pigments, diketone groups Pyrrolopyrrole pigments and the like. Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, examples of the inorganic pigment include iron, cobalt, aluminum, cadmium, lead, copper, Oxides or composite metal oxides of metals such as titanium, magnesium, chromium, zinc, antimony, and carbon black. In particular, as the above-mentioned organic pigments and inorganic pigments, specifically, compounds classified as pigments in the Outstanding Index (published by The society of Dyers and Colourists) can be cited. More specifically, examples of the organic pigment and the inorganic pigment include pigments having the following color index (C.I.) numbers, but they are not necessarily limited to these.

CI 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 Green 7, 10, 15, 25, 36, 47, and 58

The said pigment (a1) can be used individually or in combination of 2 or more types.

Among the C.I. pigments exemplified above, pigments selected from C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58 are preferably used.

The pigment is preferably a pigment dispersion liquid in which the particle diameters are uniformly dispersed. As an example of the method for uniformly dispersing the particle diameter of a pigment, the method of performing a dispersion process containing a pigment dispersant (a3), etc. are mentioned. According to this method, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

Specific examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. These can be used individually or Those who use two or more types in combination.

Dye (a2)

The dye can be used without limitation as long as it has solubility in an organic solvent. Preferably, a dye having solubility in an organic solvent and capable of ensuring reliability in solubility and solvent resistance, stability over time, and the like with respect to an alkali developing solution is preferably used.

As the dye, a dye selected from the group consisting of an acidic dye having an acidic group such as a sulfonic acid and a carboxylic acid, a salt of an acidic dye and a nitrogen-containing compound, a sulfonamide body of the acidic dye, and the like, and a derivative thereof can be used. Azo-based, xanthene-based, phthalocyanine-based acid dyes and their derivatives can also be selected.

Preferably, the dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and well-known dyes described in dyeing notes (published by Shikisensha Co., Ltd.).

As specific examples of the above dyes, as CI solvent dyes, CI solvent yellow 4, 14, 15, 16, 21, 23, 24, 38, 56, 62, 63, 68, 79, 82, 93, 94 can be cited. , 98, 99, 151, 162, 163 and other yellow dyes; CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other green dyes.

Among C.I. solvent dyes, C.I. Solvent Yellow 14, 16, 21, 56, 151, 79, and 93 which are excellent in solubility in organic solvents are preferred; Among these, C.I. Solvent Yellow 21, 79; and C.I. are more preferable.

Examples of the CI acid dye include 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, 251 and other yellow dyes; CI acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other green dyes.

Among the acid dyes, C.I. Acid Yellow 42 and C.I. Acid Green 27 which are excellent in solubility in organic solvents are preferred.

Examples of CI direct dyes include: CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141 and other yellow dyes; CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other green dyes.

Further, examples of the C.I. mordant dye include yellow dyes such as C.I. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, and the like; C.I. Mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and other green dyes.

These dyes can be used individually or in combination of 2 or more types.

Pigment dispersant (a3)

The pigment dispersant (a3) is added for deagglomeration and stability maintenance of the pigment, and substances generally used in this field can be used without limitation. Preferably, an acrylate-based dispersant (hereinafter referred to as an acrylic-based dispersant) containing BMA (butyl methacrylate) or DMAEMA (N, N-dimethylaminoethyl methacrylate) is preferably contained. At this time, the acrylic dispersant is preferably an acrylic dispersant produced by the activity control method proposed in Korean Published Patent No. 10-2004-0014311. Examples of commercially available acrylate-based dispersants produced by the above-mentioned activity control method include DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, and DISPER BYK-2150.

The acrylic dispersants exemplified above can be used individually or in combination of two or more kinds.

As the dispersant (a3), in addition to the acrylic dispersant, other resin-based pigment dispersants may be used. Examples of the other resin-based pigment dispersants include known resin-based pigment dispersants, and in particular, polycarboxylates represented by polyurethanes and polyacrylates, unsaturated polyamines, and polycarboxylic acids. , (Partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acids Oily dispersants such as esters and their modified products, or amidines or their salts formed by the reaction of a polyester having a free carboxyl group with poly (lower alkylene imine); (Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene-maleic acid copolymer, water-soluble resin such as polyvinyl alcohol or polyvinylpyrrolidone, or water-soluble polymerization Chemical compounds; polyesters; modified polyacrylates; ethylene oxide / propylene oxide addition products and phosphate esters. As a commercially available product of the resin-based dispersant, as a cationic resin dispersant, for example, BYK ( ) Company's trade names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; Trade names of BASF companies: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Trade names of Lubirzol Company: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204 / 10; Kawaken Company's trade name: (HINOACT) T-6000, T-7000, T-8000; Trade name of Ajinomoto: (AJISPUR) PB-821, PB-822, PB-823; Trade name of Kyoeisha Chemical Co., Ltd .: (FLORENE) DOPA-17HF, DOPA-15BHF, DOPA-33, DOPA-44 and so on. In addition to the acrylic dispersant, other resin-based pigment dispersants may be used alone or in combination of two or more kinds, and may be used in combination with the acrylic dispersant.

The usage-amount of the said dispersing agent (a3) is 5-60 weight part with respect to 100 weight part of solid content of the pigment (a1) used, More preferably, it is the range of 15-50 weight part. When the content of the dispersant (a3) exceeds 60 parts by weight in accordance with the above-mentioned standard, the viscosity will increase. When the content is less than 5 parts by weight, the micronization of the pigment may be difficult, or problems such as gelation may occur after dispersion.

The content of the colorant (A) is expressed in terms of a weight fraction with respect to the solid content in the colored photosensitive resin composition, and preferably contains 5 to 60% by weight, preferably 10 to 45% by weight. When the colorant (A) is contained in an amount of 5 to 60% by weight based on the above-mentioned standards, even if a thin film is formed, the color density of the pixels is sufficient, and the drop-off property of the non-pixel portion during development is not reduced, so residues are less likely to occur.

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

Alkali soluble resin (B)

The alkali-soluble resin (B) contains a chemical compound represented by Chemical Formula 1. Compounds and compounds represented by Chemical Formula 2.

In the above Chemical Formula 1, each R1 is independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

In the above Chemical Formula 2, R2 is each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

The alkali-soluble resin (B) may have an acid value of 50 to 100 mgKOH / g. In the case where the above range is not satisfied, the level required in the technical field cannot be satisfied in terms of adhesiveness and peeling characteristics, and it is difficult for the colored photosensitive resin composition to ensure a sufficient development speed, or the adhesion to the substrate is reduced, Short-circuiting of the pattern is easy to occur, the stability with time is reduced, and the viscosity is easily increased.

The weight-average molecular weight of the alkali-soluble resin may be 25,000 to 32,000 when measured by GPC. When the above range is not satisfied, the level required in the technical field cannot be satisfied in terms of adhesiveness and peeling characteristics.

In order to ensure additional developability of the alkali-soluble resin (B), a hydroxyl group may be added.

The alkali-soluble resin (B) is produced by copolymerizing an ethylenically unsaturated monomer (b1) having a carboxyl group as an essential component in order to have solubility in an alkali developing solution used in a development processing step when forming a pattern.

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 acid anhydrides of these dicarboxylic acids; mono (meth) acrylates of polymers having carboxyl and hydroxyl groups at both ends such as ω-carboxy polycaprolactone mono (meth) acrylate, etc., preferably acrylic acid and methacrylic acid .

In order to impart a hydroxyl group to the alkali-soluble resin (B), an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group can be copolymerized to produce the compound, and a compound having a glycidyl group can be produced. (b3) It is produced by additionally reacting with a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group. The compound (b3) having a glycidyl group can be additionally produced by reacting a copolymer of an ethylenically unsaturated monomer (b1) having a carboxyl group and an ethylenically unsaturated monomer (b2) having a hydroxyl group.

As specific examples of the ethylenically unsaturated monomer (b2) having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferred. Ester, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N-hydroxyethylpropenamide, and the like, and 2-hydroxyethyl (meth) acrylate is preferred. These can be used in combination of two or more kinds.

Specific examples of the compound (b3) having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, and butyric acid. Glyceryl ester, glycidyl methyl ether, ethyl glycidyl ether, glycidyl isopropyl ether, tert-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-tert-butylbenzene The formate, glycidyl stearate, aryl glycidyl ether, glycidyl methacrylate, and the like are preferred, and butyl glycidyl ether, aryl glycidyl ether, and glycidyl methacrylate are preferred. These can be used in combination of two or more kinds.

The alkali-soluble resin contains 10 to 80% by weight, and preferably 10 to 70% by weight, based on the total solid content of the colored photosensitive resin composition of the present invention. When the content is contained at the above content, the solubility in the developing solution is sufficient, the pattern formation is easy, and the film of the pixel portion of the exposed portion is prevented from being reduced during development, and the non-pixel portion has a good peeling property, which is preferable.

Photopolymerizable compound (C)

The photopolymerizable compound (C) is a light Examples of compounds that can be polymerized under the action of an initiator include monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-acrylate Hydroxyethyl, N-vinylpyrrolidone and the like.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. , Triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trihydroxy Methylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (methyl) Acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Among these, it is preferable to use a bifunctional or more polyfunctional monomer.

The photopolymerizable compound (C) is preferably contained in an amount of 5 to 50% by weight, and more preferably 7 to 50% by weight based on the total solid content of the colored photosensitive resin composition. When the content is contained at the above content, the strength and reliability of the pixel portion are improved, which is preferable.

Photopolymerization initiator (D)

The photopolymerization initiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C). In particular, the photopolymerization initiator (D) is preferably selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, and triazine-based compounds from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, price, and the like. One or more compounds among compounds, biimidazole-based compounds, oxime compounds, and thioxanthone-based compounds.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzophenone dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- (Methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2 -Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) 1- (4-morpholinophenyl) butane-1-one and the like.

Examples of the benzophenone-based compound include benzophenone, 0-benzylmethylbenzoate, 4-phenylbenzophenone, and 4-benzyl-4'-methyldiphenyl. Sulfide, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

Specific examples of the triazine-based 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-piperyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine and the like.

Specific examples of the above-mentioned biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2 , 3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole, 2,2- Bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 4,4', 5,5 'phenyl is alkoxy Carbonyl-substituted imidazole compounds and the like. Among these, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) are preferably used. ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2-bis (2,6-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1, 2'-biimidazole.

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one and the like. As commercially available products, BASF's OXE01 and OXE02 are representative. of.

Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Tons of ketones and so on.

The photopolymerization initiator (D) may further include a photopolymerization initiation aid in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. By containing the photopolymerization initiation adjuvant, the coloring photosensitive resin composition which concerns on this invention can improve sensitivity further and can improve productivity.

The photopolymerization initiation aid is preferably one or more compounds selected from, for example, an amine compound, a carboxylic acid compound, and an organic sulfur compound having a thiol group.

As the amine compound, an aromatic amine compound is preferably used, and specifically, an aliphatic amine compound such as triethanolamine, methyldiethanolamine, and triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4- Dimethylaminobenzoate, 4-dimethylaminobenzoate isoamyl, 2-dimethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate , N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as melidone), 4,4'-bis (diethylamino) Benzophenone and so on.

The carboxylic acid compound is preferably an aromatic heteroacetic acid. Specific examples include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, Dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, dimethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.

Specific examples of the organic sulfur compound having a thiol group Examples include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tri (3-mercaptobutoxyethyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetra (3-mercaptobutyrate), pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), and the like.

When the photopolymerization initiator is used together with a photopolymerization initiator, the content of the photopolymerization initiator is preferably 1 mol or less, and more preferably 0.01 to 5 mol, based on 1 mol of the photopolymerization initiator. When a photopolymerization initiation adjuvant is used at the above-mentioned content, the sensitivity of the colored photosensitive resin composition is further improved, and the productivity of a color filter formed using the composition tends to be improved, which is preferable.

The photopolymerization initiator (D) contains 0.1 to 40% by weight, preferably 1 to 30% by weight, with respect to the total solid content of the alkali-soluble resin (B) and the photopolymerizable compound (C) of the present invention. When it is contained in the above content, it is preferable to increase the sensitivity of the colored photosensitive resin composition, shorten the exposure time, improve productivity, and maintain high resolution. Moreover, the intensity | strength of the pixel part formed using the composition of the said condition, and the smoothness in the surface of the said pixel part became favorable.

Solvent (E)

The solvent (E) is not particularly limited as long as it is effective for dissolving other components contained in the colored photosensitive resin composition. As the solvent used in a general coloring photosensitive resin composition, ethers, aromatic hydrocarbons, ketones, alcohols, esters, or amines are particularly preferred.

Specific examples of the solvent (E) include ethylene glycol monoalkane such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ethers, methyl cellosolve Ethylene glycol alkyl ether acetates such as acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Alkyl glycol alkyl ether acetates such as methoxybutyl acetate, methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methyl ethyl Ketones such as ketones, acetone, methylpentyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc., 3- Ester such as ethyl ethoxypropionate and methyl 3-methoxypropionate, cyclic esters such as γ-butyrolactone and the like.

The solvent (E) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coating properties and drying properties. More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxypropionic acid Ethyl ester, methyl 3-methoxypropionate and the like.

The above-exemplified solvents (E) can be used individually or in combination of two or more kinds, and based on the total weight of the colored photosensitive resin composition of the present invention, it contains 60 to 90% by weight, preferably 70 to 85% by weight. . If the solvent (E) is in the above range of 60 to 90% by weight, a roll coater, a spin coater, a slit and spin coater, a slit coater (also sometimes referred to as a die coater), and inkjet are used. When applied by a coating device or the like, it provides the effect that the coatability becomes good.

In addition, the colored photosensitive resin composition of the present invention may further contain additives, and the additives may be optionally added as needed. Examples thereof include a curing agent, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, Anti-coagulant and so on.

The colored photosensitive resin composition of the present invention can be produced by, for example, the following method. The colorant and the solvent are mixed in advance and dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 μm or less. In this case, a pigment dispersant is used as necessary, and a part or all of the alkali-soluble resin may be blended. The remainder of the alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a reactive silicone-based surfactant are further added to the obtained dispersion (hereinafter sometimes referred to as a "kneading base"), if necessary, as necessary. The other components used, and if necessary, additional solvents are added so as to have a predetermined concentration to obtain a target coloring photosensitive resin composition.

The present invention also provides the use of the colored photosensitive resin group. Color filters made of composites.

Hereinafter, the present invention will be described in detail using synthesis examples, examples, comparative examples, and experimental examples. However, the following synthesis examples, examples, comparative examples, and experimental examples are used to illustrate the present invention. The present invention is not limited to the following synthesis examples, examples, comparative examples, and experimental examples, and various modifications and changes can be made. In addition, in the following synthesis examples, examples, and comparative examples, "%" and "parts" indicating content are based on weight unless otherwise specified.

Synthesis Example 1. Synthesis of A-1

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, and benzyl methacrylate (BZMA, chemical formula 3) 45 were charged. Parts, 58 parts of tricyclodecyl methacrylate (TCDMA, chemical formula 4), 20 parts of methacrylate, 30 parts of methacrylic acid, and nitrogen substitution. After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 15 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 80 mgKOH / g, and the weight-average molecular weight measured by GPC was 27,000 (Table 1).

[Chemical Formula 4]

Synthesis Example 2. Synthesis of A-2

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (chemical formula 4), 20 parts of methacrylate, and 32 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C., and the reaction was performed for 17 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 95 mgKOH / g, and the weight-average molecular weight measured by GPC was 30,000 (Table 1).

Synthesis Example 3. Synthesis of A-3

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (Chemical Formula 4), 20 parts of methacrylate, and 30 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 10 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized It was 31.0%, the acid value of the solid content was 80 mgKOH / g, and the weight average molecular weight measured by GPC was 20,000 (Table 1).

Synthesis Example 4. Synthesis of A-4

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (chemical formula 4), 20 parts of methacrylate, and 32 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 10 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 95 mgKOH / g, and the weight-average molecular weight measured by GPC was 20,000 (Table 1).

Synthesis Example 5. Synthesis of A-5

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (chemical formula 4), 20 parts of methacrylate, and 32 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C., and the reaction was performed for 12 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 95 mgKOH / g, and the weight-average molecular weight measured by GPC was 24,000 (Table 1).

Synthesis Example 6. Synthesis of A-6

Equipped with a stirrer, thermometer, reflux cooling pipe, drip leak 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), and 58 parts of tricyclodecyl methacrylate (chemical formula 4) were put into a 1000 ml flask with a nitrogen tube and a nitrogen introduction tube. 20 parts of methacrylate and 32 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 20 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 95 mgKOH / g, and the weight average molecular weight measured by GPC was 35,000 (Table 1).

Synthesis Example 7. Synthesis of A-7

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (Chemical Formula 4), 20 parts of methacrylate, and 34 parts of methacrylic acid were substituted with nitrogen. After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 20 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 115 mgKOH / g, and the weight-average molecular weight measured by GPC was 35,000 (Table 1).

Synthesis Example 8. Synthesis of A-8

In a 1000 ml flask equipped with a stirrer, thermometer, reflux cooling tube, dropping funnel, and nitrogen introduction tube, 400 parts of propylene glycol monomethyl ether acetate, 7 parts of AIBN, 45 parts of benzyl methacrylate (chemical formula 3), 58 parts of tricyclodecyl methacrylate (Chemical Formula 4), 20 parts of methacrylate, and 34 parts of methacrylic acid were substituted with nitrogen. Of course After stirring, the temperature of the reaction solution was raised to 120 ° C, and the reaction was allowed to proceed for 15 hours after the rise. The final solid content of the alkali-soluble resin thus synthesized was 31.0%, the acid value of the solid content was 115 mgKOH / g, and the weight average molecular weight measured by GPC was 27,000 (Table 1).

Example 1. Production of colored photosensitive resin composition

12 parts of CI Pigment Green 58 (Pigment), 1.8 parts of CI Pigment Yellow 150 (Pigment), 4.0 parts of BYK-2001 as a pigment dispersant, and 82.2 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was made using a bead mill After being sufficiently dispersed, 30 parts of alkali-soluble resin A-1 in Synthesis Example 1, 6.6 parts of polymerizable compound A9550, 1.3 parts of PBG-305 (manufacturer: TRONLY) as oxime ester initiator, and propylene glycol monomethyl 52.7 parts of ethyl ether acetate were mixed to obtain a colored photosensitive resin composition.

Example 2. Production of colored photosensitive resin composition

Except replacing the alkali-soluble resin of Example 1 with Synthesis Example 2 Except for A-2, the same composition was used to obtain a colored photosensitive resin composition.

Comparative Example 1. Production of colored photosensitive resin composition

A colored photosensitive resin composition was obtained with the same composition except that the alkali-soluble resin of Example 1 was replaced with A-3 of Synthesis Example 3.

Comparative Example 2. Production of colored photosensitive resin composition

A colored photosensitive resin composition was obtained with the same composition except that the alkali-soluble resin of Example 1 was replaced with A-4 of Synthesis Example 4.

Comparative Example 3. Production of colored photosensitive resin composition

A colored photosensitive resin composition was obtained with the same composition except that the alkali-soluble resin of Example 1 was replaced with A-5 of Synthesis Example 5.

Comparative Example 4. Production of colored photosensitive resin composition

A colored photosensitive resin composition was obtained with the same composition except that the alkali-soluble resin of Example 1 was replaced with A-6 of Synthesis Example 6.

Comparative Example 5. Production of colored photosensitive resin composition

A colored photosensitive resin composition was obtained with the same composition except that the alkali-soluble resin of Example 1 was replaced with A-7 of Synthesis Example 7.

Comparative Example 6. Production of colored photosensitive resin composition

Except replacing the alkali-soluble resin of Example 1 with Synthesis Example 8 Except for A-8, the same composition was used to obtain a colored photosensitive resin composition.

Experimental example

A color filter was produced using the colored photosensitive resin composition produced in the above-mentioned Examples 1 to 2 and Comparative Examples 1 to 6.

Specifically, each of the photosensitive resin compositions described above was applied to a BM substrate by a spin coating method, and then placed on a hot plate and maintained at a temperature of 100 ° C. for 2 minutes to form a thin film. Next, a test photomask having a pattern with a step change in transmittance in the range of 1 to 100% and a line / space pattern of 1 μm to 100 μm was placed on the film, and the distance from the test photomask was 200 μm. , Irradiate ultraviolet rays. At this time, the ultraviolet light source used a 1 KW high-pressure mercury lamp including all of the g, h, and i rays, and was irradiated at an illumination intensity of 50 mJ / cm ² without using a special optical filter. The ultraviolet-irradiated film was immersed in a KOH aqueous solution developing solution at pH 10.5 for 2 minutes to develop. The post-process baking was performed at 230 ° C for 20 minutes. The film thickness of the color filter manufactured as described above was 2.5 μm.

<Adhesiveness>

For the color filter produced above, the optical microscope of ECLIPSE LV100POL Model manufactured by Nikon was used to confirm the disappearance of the pattern of 1 μm to 100 μm in the reflection mode, and the residual pattern standard (the smaller the size of the residual pattern, the better the adhesion). The more excellent the product) was evaluated for adhesion, and the results are shown in Table 2.

<Peeling>

During the color filter manufacturing process described above, a BM substrate using UV cleaning (700 mj) was applied during spin coating to apply the photosensitive resin composition. Thereafter, with respect to the produced color filter, peeling was confirmed in a reflection mode using an optical microscope of ECLIPSE LV100POL Model manufactured by Nikon Corporation.

The criteria for judging the peeling characteristics are as follows: a standard time as shown in FIG.

As shown in Table 2, in the case of the colored photosensitive resin compositions of Examples 1 and 2, compared with Comparative Examples 1 to 6, they showed excellent results in terms of adhesion and peeling characteristics.

Claims (4)

A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The alkali-soluble resin includes a compound represented by the following Chemical Formula 1 and a compound represented by the following formula: In the compound represented by Chemical Formula 2, the weight-average molecular weight of the alkali-soluble resin is 25,000 to 32,000, and the acid value of the alkali-soluble resin is 50 to 100 mgKOH / g: In the above Chemical Formula 1, each R1 is independently hydrogen or an alkyl group having 1 to 5 carbon atoms, In the above Chemical Formula 2, each of R2 is independently hydrogen or an alkyl group having 1 to 5 carbon atoms, wherein the colorant contains one or more green pigments or green dyes and does not include xanthene dyes. The colored photosensitive resin composition according to claim 1, wherein the alkali-soluble resin includes a compound represented by the following Chemical Formula 3 and a compound represented by the following Chemical Formula 4: The colored photosensitive resin composition according to claim 1, which contains 5 to 60% by weight of the colorant and 10 to 80% by weight of the alkali-soluble based on the total weight of the solid content of the colored photosensitive resin composition. Resin, containing 5 to 50% by weight of the photopolymerizable compound, based on the total solid content of the alkali-soluble resin and the photopolymerizable compound, containing 0.1 to 40% by weight of the photopolymerization initiator, and coloring the photosensitive resin composition It contains 60 to 90% by weight of the solvent based on the total weight of the product. A color filter is manufactured using the colored photosensitive resin composition according to any one of claims 1 to 3.