KR20090121217A - Colored photosensitive resin composition - Google Patents

Abstract

PURPOSE: A colored photosensitive resin composition is provided to manufacture red color pixels with high contrast and color filters. CONSTITUTION: A colored photosensitive resin composition comprises a pigment(A), a binder resin(B), a photopolymerizable compound(C), a photopolymerization initiator(D), and a solvent(E). The pigment(A) includes C.I. pigment red 177, C.I. pigment red 242, and C.I. pigment red 254. The content of the C.I. pigment red 242 among the whole pigments is 60 weight% or less.

Description

Colored Photosensitive Resin Composition

The present invention relates to a colored photosensitive resin composition.

The color filter used for a color liquid crystal display, a color video camera, etc. is generally three colors, such as red (R), green (G), and blue (B), on a transparent substrate, such as glass, or an opaque substrate, such as silicon. It is produced by forming a transparent colored fine pattern. The transparent colored fine pattern contains colored photosensitive resin composition, and is adjusted by the kind and content of the pigment contained in a colored photosensitive resin composition.

For example, Patent Document 1 discloses C.I. Pigment Red 177 and C.I. Pigment red 242 and comprising C.I. The coloring photosensitive resin composition whose content of pigment red 242 is 65-90 weight% is disclosed.

[Patent Document 1] Japanese Patent No. 3924872

The coloring photosensitive resin composition which can manufacture a high contrast red pixel and a color filter is desired.

This invention contains a pigment (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E),

Pigment (A) is C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment containing Pigment Red 254,

C.I. in all pigments. It is a coloring photosensitive resin composition whose content of pigment red 242 is 60 weight% or less.

In addition, the present invention provides the C.I. It is the said coloring photosensitive resin composition whose content of pigment red 242 is 50 weight% or less.

In addition, the present invention provides the C.I. It is the said coloring photosensitive resin composition whose content of pigment red 242 is 35 weight% or less.

In addition, the present invention provides the C.I. It is the said coloring photosensitive resin composition whose content of pigment red 254 is 80 weight% or less.

In addition, the present invention provides the C.I. It is the said coloring photosensitive resin composition whose content of pigment red 254 is 50 weight% or less.

Moreover, this invention is a pixel formed using the said colored photosensitive resin composition.

In addition, the present invention is a color filter including the pixel.

According to the present invention, it becomes possible to manufacture high contrast red pixels and color filters.

The colored photosensitive resin composition of this invention contains a pigment (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E), and a pigment (A) is C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment red 254, comprising C.I. Content of Pigment Red 242 is 60 weight% or less.

C.I. in all pigments. It is preferable that it is 50 weight% or less, and, as for content of pigment red 242, it is more preferable that it is 35 weight% or less. Moreover, it is preferable that it is 5 weight% or more, and it is more preferable that it is 15 weight% or more. C.I. When the content of Pigment Red 242 is within the above range, a red pixel having high luminance and color purity can be formed.

C.I. in all pigments. It is preferable that it is 5 weight% or more, and, as for content of pigment red 177, it is more preferable that it is 10 weight% or more. Moreover, it is preferable that it is 95 weight% or less, and it is more preferable that it is 85 weight% or less. C.I. When the content of pigment red 177 is within the above range, a red pixel having high luminance and color purity can be formed.

C.I. in all pigments. It is preferable that content of Pigment Red 254 is 80 weight% or less, It is more preferable that it is 50 weight% or less, It is further more preferable that it is 40 weight% or less. Moreover, it is preferable that it is 5 weight% or more, and it is more preferable that it is 20 weight% or more. If it is in the said range, generation | occurrence | production of the foreign material by a thermal precipitate will become small.

In addition, the pigment (A) may contain the arbitrary pigment as a coloring pigment.

As a red pigment, C.I. Pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 180, 192, 209, 215, 216, 224, 255, 264, 265, and the like. These red pigments can be used individually or in combination of 2 or more types, respectively.

As a blue pigment, C.I. Pigment blue 15: 3, 15: 4, 76 and the like, and preferably C.I. Pigment blue 15: 3, 15: 4 and 76, more preferably C.I. Pigment blue 15: 3. These blue pigments can be used individually or in combination of 2 or more types, respectively.

As a yellow pigment, C.I. Pigment Yellow 2, 10, 13, 20, 24, 31, 53, 55, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 151, 153 , 154, 166, 173, 180 or 185, and preferably CI. Pigment yellow 83, 139, 150 is mentioned. These yellow pigments can be used individually or in combination of 2 or more types, respectively.

In addition, C.I. Pigment Green 36 or C.I. Pigment Green 7 may be added.

The content of the pigment (A) is usually 10% by weight or more and 60% by weight or less, preferably 10% by weight or more and 55% by weight or less, more preferably 15% by weight or more, based on the total amount of solids in the colored photosensitive resin composition. It is weight% or less. If the content of the pigment (A) is within the above-described range, the color concentration at the time of the color filter is sufficient, and since the required amount of the binder polymer can be contained in the composition, there is a tendency to form a pattern with sufficient mechanical strength. have.

It is preferable that binder resin (B) has alkali solubility. The binder resin (B) also serves as a dispersion medium of the pigment (A). It is preferable that the said binder resin (B) is a copolymer containing the structural unit derived from unsaturated carboxylic acid.

Specific examples of the structural unit derived from the unsaturated carboxylic acid include structural units derived from acrylic acid and structural units derived from methacrylic acid. Acrylic acid and methacrylic acid can be used individually or in combination of each. In addition to these acrylic acid and methacrylic acid, at least one carboxylic acid selected from the group consisting of other unsaturated carboxylic acids and unsaturated carboxylic anhydrides such as crotonic acid, itaconic acid, maleic acid and fumaric acid may be used in combination. It may be. Moreover, you may use together the monomer containing a hydroxyl group and a carboxyl group in the same molecule, such as (alpha)-(hydroxymethyl) acrylic acid.

It is preferable that the said binder resin (B) is a copolymer containing the structural unit derived from the above unsaturated carboxylic acid, and the structural unit copolymerizable with the structural unit derived from the said unsaturated carboxylic acid. As a structural unit copolymerizable with the structural unit guide | induced from the said unsaturated carboxylic acid, Preferably, the structural unit guide | induced from (meth) acrylic acid ester is mentioned.

As (meth) acrylic acid ester, an acrylate compound is mentioned, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids such as ethyl (meth) acrylate and aminoethyl (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclophene Tenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, mentadienyl (meth) acrylate, isobornyl (meth) acrylic Rate, pinanyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyloxyethyl (meth) acrylate, adamantyl (meth) acrylate, norbornenyl (meth) acrylate, pineinyl Esters containing alicyclic groups of unsaturated carboxylic acids such as (meth) acrylate, dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

Unsaturated carboxylic acid oxetane esters such as oxetane (meth) acrylate;

Monosaturated carboxylic acid ester of glycols, such as an oligoethylene glycol monoalkyl (meth) acrylate, etc. are mentioned, Preferably, methyl (meth) acrylate and benzyl (meth) acrylate are mentioned. Here, (meth) acrylate represents an acrylic acid ester or methacrylic acid ester.

Binder resin (B) may further contain the other structural unit copolymerizable with unsaturated carboxylic acid and acrylic acid ester. As another structural unit copolymerizable with unsaturated carboxylic acid and acrylic acid ester, Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and vinyltoluene;

Carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate;

Vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile;

And structural units derived from maleimide compounds such as N-phenylmaleimide.

These compounds mentioned above may be used independently, respectively and may be used in combination of 2 or more type.

As a structural unit copolymerizable with the structural unit derived from unsaturated carboxylic acid, the structural unit derived from (meth) acrylic acid ester is preferable, and especially the unsubstituted or substituted alkyl ester of (meth) acrylic acid, or alicyclic type of (meth) acrylic acid Preferred are structural units derived from esters comprising hydrocarbon groups.

In the binder resin (B), the structural unit derived from an unsaturated carboxylic acid is usually present in a mass fraction of 10 to 50 mass%, preferably 15 to 40 mass% in all the structural units of the copolymer. desirable. If the structural unit derived from an unsaturated carboxylic acid is 10-50 mass% based on the said reference | standard, since the solubility to a developing solution is enough, a residue will not generate | occur | produce on the board | substrate of an unexposed part, and at the time of image development, It is preferable because there is a tendency that the whole pixel does not peel off without a decrease in film.

Copolymerization is generally performed in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. Peroxide, etc. are mentioned. The solvent may be one that dissolves each monomer. For example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. Can be mentioned. What is necessary is just to determine reaction temperature in consideration of the decomposition temperature of a polymerization initiator, the boiling point of a solvent, a monomer, etc. Moreover, the side chain of the copolymer obtained in this way can also be modified to the compound which has a photosensitive group, and it can also be set as photosensitive binder resin (B). At this time, a catalyst for introducing a photosensitive group may be added to the resin. As a catalyst, tris dimethylamino methyl phenol is mentioned, for example. In addition, additives for preventing side reactions may be added. As an additive, hydroquinone is mentioned, for example.

It is preferable that the weight average molecular weights of polystyrene conversion of binder resin (B) are 5,000-100,000, More preferably, it is 7,000-50,000. When the polystyrene reduced weight average molecular weight of the binder resin (B) is 5,000 to 100,000, film reduction is less likely to occur at the time of development, and is preferable since the missing property of the non-pixel portion at the time of development tends to be good.

Binder resin (B) is 5-90 mass% normally with respect to the total solid amount in a coloring photosensitive resin composition, Preferably it contains 10-70 mass%. When content of the said binder resin (B) is 5-90 mass% on the said reference | standard, the solubility to a developing solution is enough, a developing residue hardly arises on the board | substrate of a non-pixel part, and the film | membrane of the pixel part of an exposure part at the time of image development is carried out. It is preferable because a decrease hardly occurs, and the omission of non-pixel portions tends to be good.

The photopolymerizable compound (C) contained in the coloring photosensitive resin composition of this invention is a compound which produces superposition | polymerization by action of a light and a photoinitiator (D), For example, the compound which has a carbon-carbon unsaturated bond corresponds. . As said photopolymerizable compound (C), a monofunctional monomer, a bifunctional monomer, and another polyfunctional monomer are mentioned.

As a specific example of a monofunctional monomer, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone Etc. can be mentioned.

Moreover, as a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate And bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and the like.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tris (methacryloyloxyethyl) isocyanurate, and the like.

The photopolymerizable compound (C) Examples of particularly, acrylic group (CH ₂ = CHCO-) to have, much is per unit weight of the rider acrylic compound, in other words, an acryl group acrylic group represented by one equivalent of compound per gram of water can It is preferable that the equivalent is small, and the compound whose acrylic group equivalent is 100 or less is especially preferable. When an acryl group equivalent becomes large, since sensitivity is not enough at the time of exposure or image development, it may lead to the productivity fall of a color filter. Examples of the monomer having an acrylic group equivalent of 100 or less include ethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like. Preferably trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc. are mentioned. Moreover, as a photopolymerizable compound (C), a bifunctional monomer and another polyfunctional monomer are preferable.

Content of a photopolymerizable compound (C) is 1-60 mass parts normally with respect to a total of 100 mass parts of binder resin (B) and a photopolymerizable compound (C) in a coloring photosensitive resin composition, Preferably it is 5-50 mass parts. . If content of a photopolymerizable compound (C) is the said range, there exists a tendency for the intensity | strength, pattern shape, and smoothness of a pixel part to become favorable, and it is preferable.

As a photoinitiator (D), the active radical generator which generate | occur | produces an active radical when light is irradiated, the acid generator which generate | occur | produces an acid, etc. are mentioned. Examples of the active radical generator include acetophenone photopolymerization initiators, benzoin photopolymerization initiators, triazine photopolymerization initiators, benzophenone photopolymerization initiators, oxime photopolymerization initiators, and the like.

As an acetophenone type photoinitiator, 2-methyl-2- morpholino-1- (4-methylthiophenyl) propane- 1-one, diethoxy acetophenone, 2-hydroxy-2- methyl-, 1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane And oligomers of -1-ones.

As a benzoin type photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a triazine photoinitiator, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl), for example. -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-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) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Romethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As a benzophenone type photoinitiator, a benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra (tert-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethyl benzophenone, etc. are mentioned.

As an oxime type compound, an O-acyl oxime type compound is mentioned, for example, As a specific example, 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzo Ate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione2-oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] ethanone 1-O-acetate, 1- [9-ethyl-6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl)- 9H-carbazol-3-yl] ethanone 1-O-acetate, and the like.

As active radical generators other than the above examples, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5' -Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titano Sen compounds; and the like.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo Nate, 4-acetoxyphenylmethyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfo Onium salts, such as a nitrate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

In addition, among the compounds described above as an active radical generating agent, there are also compounds which generate an acid simultaneously with the active radical. For example, an active radical generating agent such as a triazine photopolymerization initiator can be used as an acid generator.

These photoinitiators (D) can be used individually or in combination of 2 types or more, respectively.

A photoinitiator (D) can also be used combining the photoinitiator. As said photopolymerization start adjuvant, an amine compound, a thiol group containing compound, and a carboxylic acid compound are preferable, and an aromatic amine compound is more preferable as an amine compound.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid 2 -Ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Heiler Ketone), 4,4'-bis (diethylamino) benzo And aromatic amine compounds such as phenone.

A thiol group containing compound is a compound which has a thiol group in a molecule | numerator, As a thiol compound which has one thiol group, 2-mercapto benzothiazole, 2-mercaptobenzoxazole, etc. are mentioned, Aliphatic which has two or more thiol groups in an aliphatic group Examples of the polyfunctional thiol compound include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane trithioglycolate , Butanediol bisthio propionate, trimethylol propane tristyroopionate, trimethylol propane tristhioglycolate, pentaerythritol tetrakistielopionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl trithio Propionate, and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichlorophenyl Thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Moreover, in addition to these, the thioglycolate of a polyhydric hydroxy compound, a thio propionate, etc. are mentioned, As a thio propionate of a preferable polyhydric hydroxy compound, a trimethylol propane tristyopiopioneate and a trimethylol propane trithio glycol Laterate and pentaerythritol tetrakistiopionate.

Content of a photoinitiator (D) is 0.1-40 mass parts normally with respect to a total of 100 mass parts of binder resin (B) and a photopolymerizable compound (C), Preferably it is 1-30 mass parts. The content of the photopolymerization start adjuvant is usually 0.1 to 50 parts by mass, preferably 1 to 40 parts by mass with respect to 100 parts by mass in total of the binder resin (B) and the photopolymerizable compound (C).

The solvent (E) may be various ones used in this field. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

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

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

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of a solvent (E) is 60-90 mass% normally with a mass fraction with respect to the whole coloring photosensitive resin composition, Preferably it is 70-85 mass%. When content of the said solvent (E) is the said range, since applicability | paintability tends to become favorable, it is preferable.

The coloring photosensitive resin composition of this invention may further contain additives (F), such as a filler, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, surfactant, another high molecular compound.

Specific examples of the filler include glass, silica, alumina, and the like.

Commercially available pigment dispersants can be used as the pigment dispersant, for example, surfactants such as silicone, fluorine, ester, cation, anionic, nonionic, and amphoteric and the like can be cited. It is used combining a species or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethylene imines, and the like. In addition, KP (produced by Shin-Etsu Chemical Co., Ltd.), polyflow (Kyoei Chemical Co., Ltd.), F-Top (made by Tochem Products Co., Ltd.), Megafax (Daintbone Ink Chemical Industries, Ltd.) ) Manufactured), fluoride (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Suplon (above, manufactured by Asahi Glass Co., Ltd.), Solsperth (manufactured by Abysia Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.) ), PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercapto Propyl trimethoxysilane, etc. are mentioned.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.

As surfactant, surfactant which has a fluorine atom or a silicon atom is preferable. Specifically, 1 or more types chosen from the group which consists of a silicone type surfactant, a fluorine type surfactant, and a silicone type surfactant which has a fluorine atom are mentioned.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper 29SHPA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: Toray Silicon Co., Ltd.), KP321, KP322, KP323, KP324 And KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Japan Japan).

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride (trade name) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), mega pack (brand name) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F489, copper F554 , Copper R30 (manufactured by DIC Corporation), F-top (brand name) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Suplon (brand name) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine K. K. Gen. Sho), BM-1000, BM-1100 (all manufactured by BM Chemie Co., Ltd.), and the like.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), and the like can be given.

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

Specific examples of the other polymer compound include thermosetting resins such as epoxy resins, thermoplastic resins such as polyesters and polyurethanes, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, and polyfluoroalkyl acrylates.

The coloring photosensitive resin composition of this invention can be manufactured as follows, for example. That is, the pigment (A) is previously mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, a pigment dispersant is used as needed and one part or all part of binder resin (B) may be mix | blended. The remaining concentration of the binder resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D), other components used as needed, and further solvents as necessary, are added to the obtained dispersion (mill base). It adds so that it may obtain the target coloring photosensitive resin composition.

Thus, the colored photosensitive resin composition manufactured can be apply | coated on a base material as follows, photocuring and developing, and it can be set as a colored pixel. First, this composition is spin-coated on a board | substrate (usually glass), and heat-drying (prebaking) removes a solvent and obtains a smooth coating film. The thickness of the coating film at this time is about 1-3 micrometers. The ultraviolet-ray is irradiated to the coating film obtained in this way through the negative mask for forming the target image. At this time, it is preferable to use an apparatus such as a mask aligner so that the parallel light beam is uniformly irradiated to the entire exposure portion and the alignment of the mask and the substrate is accurately performed. In addition, the target pixel is obtained by contacting the coating film which hardened | cured after this to a alkali solution of alkali, melt | dissolving a non-exposed part, and developing. After image development, you may perform post-curing (post baking) about 10 to 60 minutes at 150-230 degreeC as needed.

The developing solution used for image development after patterning exposure is the aqueous solution containing an alkaline compound and surfactant normally.

As an alkaline compound, an inorganic and organic alkaline compound is mentioned. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium bicarbonate And potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

In addition, specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine, etc. are mentioned. These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

Moreover, a nonionic surfactant, anionic surfactant, or cationic surfactant is mentioned as surfactant in alkaline developing solution.

Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, and poly Oxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Specific examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate or dode Alkyl aryl sulfonates, such as sodium cinnaphthalene sulfonate, etc. are mentioned.

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

These surfactants may be used alone, or two or more kinds thereof may be used in combination.

The density | concentration of surfactant in alkaline developing solution is 0.01-10 mass% normally, Preferably it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

The pixels corresponding to the color of the colored component in the colored photosensitive resin composition are obtained through the application of the colored photosensitive resin composition, drying, patterning exposure to the resulting dried coating film, and development, and these operations are required for the color filter. The color filter is obtained by repeating by the number of colors used. That is, the color filter can normally arrange three primary color pixels of red, green, and blue on a substrate.

A red pixel is formed using the coloring photosensitive resin composition of this invention. It is preferable that the coordinate values of x and y in a CIE chromaticity diagram are 0.500 <x <0.690, 0.280 <y <0.340, and, as for the said red pixel, it is more preferable that it is 0.520 <x <0.680, 0.290 <y <0.340.

According to the present invention, it becomes possible to manufacture high contrast red pixels and color filters.

The color filter containing the pixel obtained using the coloring photosensitive resin composition of this invention can be used suitably for various display apparatuses, for example, liquid crystal display devices, such as a monitor and a television.

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are weight% and a weight part, unless there is a special mention.

<Synthesis of Binder Resin (B1)>

133 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 ° C, dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Kasei Kogyo Co., Ltd.) 22.0 g (0.10 mol), benzyl methacrylate 82.8 g (0.47 mol), A mixture containing 37.0 g (0.43 mol) of methacrylic acid, 3.6 g of 2,2'-azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate was added dropwise into the flask over 2 hours using a dropping funnel. After completion of the dropwise addition, the mixture was stirred at 100 ° C for 5 hours.

After completion of stirring, air was introduced into the flask through a gas introduction tube, and the atmosphere in the flask was replaced with air, followed by 21.5 g (0.15 mol) of glycidyl methacrylate, 0.9 g of trisdimethylaminomethylphenol, and 0.145 of hydroquinone. g was thrown into the flask, and reaction was continued at 110 degreeC for 6 hours, and the binder resin (B1) of 37.8 mass% of solid content and 97 mgKOH / g of acid value was obtained.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually titrated using an aqueous potassium hydroxide solution having a known concentration. Obtained by

The weight average molecular weight of polystyrene conversion measured by GPC method of the following conditions of obtained binder resin (B1) was 9,000.

Device; HLC-8120 GPC (manufactured by Tosoh Corporation)

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 mL / min

Test liquid solids concentration; 0.001 to 0.01 mass%

Injection amount; 50 μL

Detectors; RI

Calibration standards; TSK standard polystyrene (TSK STANDARD POLYSTYRENE) F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Other components used in this example are shown in Table 1.

(Example 1)

Each component was mixed so that it might become a composition shown in Table 2, and the coloring photosensitive resin composition 1 was obtained. The coating film was evaluated by the following method using the obtained coloring photosensitive resin composition 1.

<Preparation of coating film for evaluation>

A glass substrate (# 1737; manufactured by Corning) on a 2-inch side was washed sequentially with a neutral detergent, water, and alcohol, and then dried.

The colored photosensitive resin composition 1 was apply | coated by this spin coating method on this glass substrate, and then prebaked for 3 minutes at 100 degreeC in a clean oven.

After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), the light was irradiated at an exposure dose of 365 mJ / cm ² (365 nm) in an air atmosphere, and heated at 220 ° C. for 20 minutes to provide an evaluation coating film. Prepared.

<Evaluation of the act>

About the coating film for evaluation, film thickness was measured using a film thickness meter (DEKTAK; Veeco Co., Ltd.), and chromaticity (x, y) and lightness (OSP-SP200; OLYMPUS Co., Ltd.) were used. Y) was measured. In addition, the contrast value was measured as 10000 using the contrast measuring device (CT-1; Tsubasaka Denki Co., Ltd.). The results are shown in Table 3.

(Examples 2 to 6)

Colored photosensitive resin composition was obtained like Example 1 so that it may become a composition shown in Table 4. Table 5 shows the results of the evaluation performed in the same manner as in Example 1.

According to the present invention, it becomes possible to manufacture high contrast red pixels and color filters.

Claims (7)

Pigment (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) are included, Pigment (A) is C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment containing Pigment Red 254, C.I. in all pigments. The coloring photosensitive resin composition whose content of pigment red 242 is 60 weight% or less. The method of claim 1, wherein the C.I. in the whole pigment. The coloring photosensitive resin composition whose content of pigment red 242 is 50 weight% or less. The C.I. composition according to claim 1 or 2, wherein the C.I. The coloring photosensitive resin composition whose content of pigment red 242 is 35 weight% or less. A C.I. composition according to any one of claims 1 to 3, in all pigments. The coloring photosensitive resin composition whose content of pigment red 254 is 80 weight% or less. The C.I. compound according to any one of claims 1 to 4, in all pigments. The coloring photosensitive resin composition whose content of pigment red 254 is 50 weight% or less. The pixel formed using the coloring photosensitive resin composition of any one of Claims 1-5. The color filter containing the pixel of Claim 6.