JP2003255524A - Colored photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive composition having small dependence of pattern size on light exposure, a color filter using the colored photosensitive composition and a liquid crystal display. <P>SOLUTION: The colored photosensitive composition comprises (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent and (F) a phosphorus-base antioxidant. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a colored photosensitive composition.

[0002]

2. Description of the Related Art A colored photosensitive composition, which is a photosensitive composition colored with a colorant, is used to form color pixels or a black matrix that form a color filter of a color liquid crystal display device, a color solid-state imaging device, or the like. It is known that it is useful as a raw material of (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound (D) a photopolymerization initiator and (E) a solvent. Further, JP-A-2002-22925 discloses that a colored photosensitive resin composition for a color filter containing a hindered phenolic antioxidant is excellent in pattern dimensional stability under specific exposure conditions. ing.

[0003]

However, when the conventional colored photosensitive composition is used for the production of a color filter, the sensitivity tends to be high, so that the entire surface is easily exposed and a pattern may not be obtained in some cases. . Therefore, there has been a problem that when the amount of the photopolymerization initiator is reduced in order to reduce the sensitivity, the dependency of the pattern size on the exposure amount becomes large. for that reason,
Although it was necessary to accurately control the exposure amount in order to form a pattern having a constant size, such accurate control was difficult in practice. An object of the present invention is to provide a colored photosensitive composition in which the pattern size has little exposure dose dependency.

[0004]

Therefore, as a result of diligent studies, the present inventor has made (A) a colorant, (B) a binder polymer, (C) a photopolymerizable compound (D) a photopolymerization initiator, and (E). In the conventional colored photosensitive composition comprising a solvent, (F)
The present inventors have found that the colored photosensitive composition obtained by adding a phosphorus-based antioxidant can form a colored pattern having a small exposure dose dependency, and thus reached the present invention. That is, the present invention includes (A) a colorant, (B) a binder polymer,
From (C) a photopolymerizable compound, (D) a photopolymerization initiator, (E) a solvent and (F) a phosphorus-based antioxidant, a colored photosensitive composition characterized by comprising: Is applied onto a substrate or a layer consisting of the solid content of the colored photosensitive composition already formed, the volatile components are removed from the applied colored photosensitive composition, and the layer is exposed through a photomask. The present invention provides a method for forming a colored pattern to be developed, a color filter manufactured by the manufacturing method, and a liquid crystal display device including the color filter.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The colorant (A) contained in the colored photosensitive composition of the present invention may be an organic colorant which is an organic substance or an inorganic colorant which is an inorganic substance. .
The organic colorant may be a pigment, a dye, or a natural pigment. Inorganic colorants are metal oxides, metal complex salts, inorganic salts of barium sulfate (extensive pigments)
Inorganic pigments such as Among these colorants, organic colorants and organic pigments are preferably used because of their excellent heat resistance and color developability. Specific examples of organic pigments and inorganic pigments include the color index (The So
Published by ciety of Dyers and Colorists (P
igment). Specifically, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I.
I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 20, C.I. I.
Pigment Yellow 24, C.I. I. Pigment Yellow 31, C.I. I. Pigment Yellow 53, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 8
6, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 10
9, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 1
25, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I.
Pigment Yellow 147, C.I. I. Pigment Yellow 148, C.I. I. Pigment Yellow 150, C.I.
I. Pigment Yellow 153, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 166,
C. I. Pigment Yellow 173, CI Pigment Yellow 194, CI Pigment Yellow 214, and the like, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 3
6, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 42,
C. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I.
I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I.
Pigment Orange 65, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73, C.I. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 105,
C. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144, C.I.
I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 168, C.I. I.
Pigment Red 176, C.I. I. Pigment Red 1
77, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 20
9, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 224,
C. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264, C.I.
I. Pigment Red 265 and other red pigments, C.I. I.
Pigment Blue 15, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 15: 4, C.I. I.
Pigment Blue 15: 6, C.I. I. Pigment Blue 60, a blue pigment such as C.I. I. Pigment Violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32,
C. I. Pigment Violet 36, C.I. I. Pigment Violet 38, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36,
C. I. Pigment Green 37, a green pigment such as C.I.
I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. Pigment Black 1, C.I. I. Pigment Black 7 and other black pigments. Preferred pigments include C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 150, C.I. I. Pigment Red 177, C.I. I. Pigment Red 20
9, C.I. I. Pigment Red 254, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15:
6, C.I. I. Pigment Violet 23, C.I. I. Pigment Green 36. These organic pigments and inorganic pigments may be used alone, or 2
You may mix and use 1 or more types. Of these organic pigments and inorganic pigments, organic pigments are, if necessary, rosin-treated, surface-treated with a pigment derivative having an acidic group or basic group introduced, or grafted onto the pigment surface with a polymer compound or the like. Treatment, atomization treatment by sulfuric acid atomization method, etc.
Alternatively, cleaning treatment with an organic solvent or water for removing impurities may be performed. The content of colorant is
It is usually 1 by mass fraction based on the total solid content of the colored photosensitive composition.
Mass% or more and 60 mass% or less, preferably 3 mass% or more 5
It is used in the range of 0 mass% or less.

As the binder polymer (B), a polymer which can disperse a colorant and imparts to the colored photosensitive composition layer a function of removing a region not irradiated with light rays during development and leaving a region irradiated with light rays is used. To be done. The binder polymer is preferably a polymer composed of a monomer unit having a carboxyl group, for example. Examples of the monomer having a carboxyl group include at least 1 in the molecule of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
Examples of the unsaturated carboxylic acid having one carboxyl group include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. These monomers having a carboxyl group are compounds having a carbon-carbon unsaturated bond and can be used alone or in combination of two or more kinds. The binder polymer is preferably a copolymer of the monomer having the carboxyl group and another monomer. The other monomer is a monomer having a carbon-carbon unsaturated bond and capable of copolymerizing with a monomer having a carboxyl group,
Specifically, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methyl (meth) acrylate or ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl. Unsaturated carboxylic acid ester compounds such as (meth) acrylate, unsaturated carboxylic acid aminoalkyl ester compounds such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate, vinyl acetate,
Carboxylic acid vinyl ester compounds such as vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile, 3-methyl-3
-(Meth) acryloxymethyl oxetane, 3-ethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3
Unsaturated carboxylic acid oxetane ester compounds such as -methyl-3- (meth) acryloxyethyl oxetane. These monomers are used alone or in combination of two or more. Examples of the copolymer include benzyl methacrylate / methacrylic acid copolymer, styrene / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer, 3-ethyl-3. −
Methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid / styrene copolymer and the like can be mentioned. In particular,
A benzyl methacrylate / methacrylic acid copolymer is preferred. The content of the monomer unit having a carboxyl group in the copolymer is 5 to 50% by mass fraction, preferably 1
It is 0 to 40%. The binder polymer has a weight average molecular weight of 5,000 as determined by gel permeation chromatography (GPC) using polystyrene as a standard.
In the range of 0 to 400,000, and even 10,000 to 3
It is preferably in the range of 0,000. The binder polymer is used in a mass fraction of generally 5 to 90%, preferably 20 to 70%, based on the total solid content of the photosensitive composition.

The photopolymerizable compound (C) is an active radical generated from a photopolymerization initiator upon irradiation with light,
A compound that can be polymerized with an acid or the like, and examples thereof include a compound having a polymerizable carbon-carbon unsaturated bond.
The compound may be a monofunctional photopolymerizable compound or a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound. Examples of the monofunctional photopolymerizable compound include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Examples of the bifunctional photopolymerizable compound include 1,
6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3- Examples include methylpentanediol di (meth) acrylate. Examples of the trifunctional or higher photopolymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa. (Meth) acrylate etc. are mentioned. A preferred photopolymerizable compound is dipentaerythritol hexa (meth) acrylate. The photopolymerizable compounds may be used alone or in combination of two or more, but bifunctional or higher functional photopolymerizable compounds are preferably used, and when two or more photopolymerizable compounds are used, at least one is It is preferable to use a bi- or higher functional photopolymerizable compound. The amount of the photopolymerizable compound used is usually 0.1 part by mass or more and 70 parts by mass or less, preferably 1 part by mass or more and 60 parts by mass or less, per 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

Examples of the photopolymerization initiator (D) include active radical generators that generate active radicals when irradiated with light. For example, acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, Examples thereof include triazine compounds. Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal,
2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-
2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) butan-1-one, 2
Examples thereof include an oligomer of -hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. As the benzoin compound, for example,
Examples thereof include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone compound include benzophenone and o
-Methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6
-Trimethylbenzophenone and the like. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone,
2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be mentioned. As a triazine-based compound,
For example, 2,4-bis (trichloromethyl) -6- (4
-Methoxyphenyl) -1,3,5-triazine, 2,
4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- (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 (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3 , 5-triazine and the like. As the active radical generator, 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, phenylglyoxyl Methyl acid, a titanocene compound, etc. can also be used. A commercially available product may be used as the active radical generator. Examples of commercially available photopolymerization initiators include trade name “Irgacure-907” (acetophenone photopolymerization initiator, manufactured by Ciba Specialty Chemicals). These photopolymerization initiators can be used alone or in combination of two or more kinds. The amount of the photopolymerization initiator used is usually 1 part by mass or more and 30 parts by mass or less, preferably 3 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound.

The colored photosensitive composition of the present invention may contain a photopolymerization initiation auxiliary agent. The photopolymerization initiation aid is a compound used in combination with the photopolymerization initiator to accelerate the polymerization of the photopolymerizable compound initiated by the photopolymerization initiator. Examples of the photopolymerization initiation aid include amine compounds and alkoxyanthracene compounds. Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like.
2-Dimethylhexyl 4-dimethylaminobenzoate, N,
N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly called Michler's ketone),
4,4'-bis (diethylamino) benzophenone,
4,4'-bis (ethylmethylamino) benzophenone and the like can be mentioned. Examples of the alkoxyanthracene compounds include 9,10-dimethoxyanthracene and 2
-Ethyl-9,10-dimethoxyanthracene, 9,1
0-diethoxyanthracene, 2-ethyl-9,10-
Examples thereof include diethoxy anthracene. A commercially available photopolymerization initiation aid may be used, and examples of the commercially available photopolymerization initiation aid include "EAB-F" (trade name, manufactured by Hodogaya Chemical Co., Ltd.). When the photopolymerization initiator aid is used, the amount used is usually 10 mol or less, preferably 0.01 mol or more and 5 mol per mol of the photopolymerization initiator.
It is less than or equal to mol. When the photopolymerization initiator and the photopolymerization initiation auxiliary agent are used, the total amount thereof is usually 1 part by mass or more and 30 parts by mass or less, preferably 100 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. It is 3 parts by mass or more and 20 parts by mass or less.

The colored photosensitive composition of the present invention contains (E) a solvent. Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, and other ethylene glycol monoalkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol diethyl ether. Diethylene glycol dialkyl ethers such as butyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Chromatography ether acetate, methoxybutyl acetate, alkylene glycol alkyl ether acetates such as methoxy pentyl acetate,
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, aromatic aliphatic ethers such as anisole, phenetole and methylanisole, acetone, 2-
Butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, ketones such as cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, alcohols such as glycerin, 3- Examples thereof include esters such as ethyl ethoxypropionate, methyl 3-methoxypropionate, ethyl lactate and methyl 2-hydroxyisobutyrate, and cyclic esters such as γ-butyrolactone. These solvents may be used alone or in combination of two or more, and the content of the solvent in the colored photosensitive composition is usually 5 in terms of mass fraction.
It is used so as to be 0 mass% or more and 90 mass% or less, preferably 60 mass% or more and 85 mass% or less.

As the phosphorus-based antioxidant (F), a known phosphorus-based antioxidant can be used. Examples of the phosphorus-based antioxidant include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy].
-2,4,8,10-Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4, 4 '
-Butylidene-bis (3-methyl-6-t-butylphenylditridecyl) phosphite, octadecylphosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,1
0-dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phos Fafenanthrene-10-
Oxide, 10-decyloxy-9,10-dihydro-
9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-t-butylphenyl)
Phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite,
Cyclic neopentanetetraylbis (2,6-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (2,4-di) -T-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis [2,4-bis (1 , 1-
Dimethylethyl) -6-methylphenyl] ethyl ester, phosphonic acid, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and the like can be mentioned, preferably 6- [3- (3-t -Butyl-4
-Hydroxy-5-methylphenyl) propoxy]-
2,4,8,10-tetra-t-butyldibenz [d,
f] [1,3,2] dioxaphosphine, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and the like. The phosphorus-based antioxidant can be used alone or in a mixture. When mixed and used, the ratio can be appropriately selected depending on the kind and addition amount of the colorant, the kind and addition amount of the photopolymerization initiator, the manufacturing conditions of the color pixel, and the like. The amount of the phosphorus-based antioxidant to be used can be appropriately selected depending on the type and amount of colorant, the type and amount of photopolymerization intervening, the manufacturing conditions of the color pixel, etc. Normally, the mass fraction is 0.
01% to 30%, preferably 0.05% to 10
% Or less, particularly preferably 0.1% or more and 5% or less.

The colored photosensitive composition of the present invention may contain other additives. As the additive, for example,
Examples include fillers, polymer compounds other than binder polymers, surfactants, adhesion promoters, aggregation inhibitors, organic acids, organic amino compounds, and curing agents.

Examples of the filler include glass and alumina.

Examples of the polymer compound other than the binder polymer include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate and the like.

Examples of the surface active agent include nonionic surface active agents, cationic surface active agents, anionic surface active agents and amphoteric surface active agents.

Examples of the adhesion promoter 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-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned. .

Examples of the anticoagulant include sodium polyacrylate and the like.

Examples of the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and caprylic acid, oxalic acid and malonic acid. , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, Aliphatic dicarboxylic acids such as itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid, tricarballylic acid,
Aliphatic tricarboxylic acids such as aconitic acid, camphoronic acid, benzoic acid, toluic acid, cuminic acid, hemelitic acid,
Examples thereof include aromatic monocarboxylic acids such as mesitylene acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melophanoic acid and pyromellitic acid.

As the organic amino compound, for example, n-
Propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butyl, t-butylamine, n-pentylamine, n-hexylamine, n-
Monoalkylamines such as heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4- Monocycloalkylamines such as methylcyclohexylamine, methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di n-propylamine, di i-propylamine, di n-butylamine, di i
-Butylamine, s-diec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine and other dialkylamines, methylcyclohexylamine, ethylcyclohexylamine and other monoalkylmonocycloalkylamines, dicyclohexylamine Such as dicycloalkylamines, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine,
Methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri-n-butylamine, tri-i-butylamine, trisec-butylamine, tri-t-butylamine, tri-n-pentylamine, Trialkylamines such as tri-n-hexylamine, dimethylcyclohexylamine,
Dialkylmonocycloalkylamines such as diethylcyclohexylamine, monoalkyldicycloalkylamines such as methyldicyclohexylamine and ethyldicyclohexylamine, tricycloalkylamines such as tricyclohexylamine, 2-aminoethanol, 3-amino-1 -Propanol, 1-amino-2
-Monoalkanolamines such as propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino-1-
Monocycloalkanolamines such as cyclohexanol, diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-butanolamine, di-n-pentanolamine dialkanolamines, di-n- Dialkanolamines such as hexanolamine, dicycloalkanolamines such as di (4-cyclohexanol) amine,
Triethanolamine, tri-n-propanolamine,
Tri-alkanolamines such as tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine and tri-n-hexanolamine, tricycloalkanols such as tri (4-cyclohexanol) amine Amines, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethyl Amino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-
Aminoalkanediols such as 1,3-propanediol, 4-amino-1,2-cyclohexanediol,
Aminocycloalkane diols such as 4-amino-1,3-cyclohexanediol, 1-aminocyclopentanone methanol, amino group-containing cycloalkanone methanols such as 4-aminocyclopentanone methanol, 1-aminocyclohexanone methanol, Amino group-containing cycloalkanemethanols such as 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol and 4-diethylaminocyclohexanemethanol,
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-
Aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclopropanecarboxylic acid, 1
-Aminocarboxylic acids such as aminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid, aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi -Propylaniline, pn-butylaniline, pt-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline,
Aromatic amines such as N, N-diethylaniline, p-methyl-N, N-dimethylaniline, o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p -Aminobenzyl alcohols such as diethylaminobenzyl alcohol, o-aminophenol, m-aminophenol, p-aminophenol, p
-Aminophenols such as dimethylaminophenol and p-diethylaminophenol, and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

The curing agent is used to cure the color pixels and the like by heat treatment after development to improve the mechanical strength thereof. Examples of such a curing agent include compounds capable of reacting with the carboxyl group of the binder polymer to crosslink the binder polymer when heated, and the binder polymer is crosslinked to cure the color pixels and the like. Further, it may be a compound which can be polymerized by itself when heated, and when it is polymerized alone, color pixels and the like are cured. Examples of such compounds include epoxy compounds and oxetane compounds.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac type epoxy resin, and other aromatic epoxy resins. , Alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester resin, glycidyl amine resin, epoxy resin such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resin and other than brominated derivatives thereof Of aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)
Polymer epoxide, isoprene (co) polymer epoxide, glycidyl (meth) acrylate (co)
Examples thereof include polymers and triglycidyl isocyanurate.

Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane,
Examples thereof include adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylic acid bisoxetane.

The colored photosensitive composition of the present invention may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound together with the curing agent. Examples of such compounds include polyvalent carboxylic acids, polycarboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4 and
5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4
Aromatic polycarboxylic acids such as 4′-benzophenonetetracarboxylic acid, succinic acid, glutaric acid, adipic acid,
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and itaconic acid, hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid,
Examples thereof include alicyclic polycarboxylic acids such as cyclopentane tetracarboxylic acid and 1,2,4,5-cyclohexane tetracarboxylic acid. Examples of polyvalent carboxylic acid anhydrides include aromatic polyvalent carboxylic acids such as phthalic anhydride, pyromellitic dianhydride, trimellitic dianhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Aliphatic polyhydric compounds such as acid anhydrides, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride. Carboxylic anhydrides, hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclo Pentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic acid anhydride, nadi anhydride Alicyclic polycarboxylic acid anhydrides such as acid, ethylene glycol bis trimellitate acid, an ester group-containing carboxylic acid anhydrides such as glycerin tris trimellitate anhydride. As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As such an epoxy resin curing agent, for example, a trade name "ADEKA HARDNER EH-700" (Asahi Denka Kogyo Co., Ltd.)
Product name, "Rikacid HH" (New Japan Rika Co., Ltd.)
Product), product name "MH-700" (manufactured by Shin Nippon Rika Co., Ltd.)
And so on. These curing agents can be used alone or in combination of two or more.

The colored photosensitive composition of the present invention comprises, for example, a colorant in a solvent, a binder polymer, a photopolymerizable compound,
It can be produced by mixing a photopolymerization initiator and a phosphorus-based antioxidant, and when an additive is contained, it may be mixed in a solvent.

As a method of forming a pattern using the colored photosensitive composition of the present invention, specifically, the colored photosensitive composition of the present invention is applied to a substrate or a solid colored layer previously formed on the substrate. A volatile component such as a solvent is removed from the coated photosensitive composition layer (hereinafter, this may be referred to as a substrate, etc.) by coating, and the volatile component is removed through a photomask. A method in which the removed layer is exposed and then developed is included.

As the substrate, for example, a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate,
Substrates having a flat surface such as an aromatic polyamide substrate, a polyamide-imide substrate, and a polyimide substrate can be given. Such a substrate may be subjected to a pretreatment such as a chemical treatment with a chemical such as a silane coupling agent, a plasma treatment, an ion plating treatment, a sputtering treatment, a vapor phase reaction treatment, or a vacuum vapor deposition treatment. When a silicon substrate or the like is used as the substrate, a charge coupled device (CCD), a thin film transistor (TFT, Thin F) is formed on the surface of the silicon substrate or the like.
ilm Transistor) or the like may be formed.

To apply the colored photosensitive composition onto the substrate, for example, the colored photosensitive composition of the present invention is applied by spin coating (spin coating), cast coating, roll coating, slit & It may be applied on a substrate or the like by a usual application method such as a spin coating method, and then a volatile component such as a solvent may be volatilized by heating. In this way, a layer made of the solid content of the colored photosensitive composition is formed on the substrate or the like.

Next, a layer made of the solid content of the colored photosensitive composition (hereinafter, this may be referred to as a colored photosensitive composition layer) is exposed. To expose, for example, a light beam may be applied through a photomask. As a ray of light,
Ultraviolet rays called g-line (wavelength 436 nm) and i-line (wavelength 365 nm) are used. The light rays are emitted through a photomask, where the photomask is, for example,
A glass plate is provided with a light-shielding layer that shields light rays. The portion of the glass plate where the light-shielding layer is not provided is a light-transmitting portion through which light rays are transmitted, and the colored photosensitive composition layer is exposed in a pattern according to the pattern of this light-transmitting portion, and the light rays are irradiated. A non-irradiated area that has not been irradiated and an irradiated area that has been irradiated with light rays are generated. The irradiation amount of light in the irradiation region, the weight average molecular weight of the binder polymer, the monomer ratio, the content, the type and content of the photopolymerizable compound, the type and content of the photopolymerization initiator, of the photopolymerization initiation aid It is appropriately selected depending on the type and content.

The colored photosensitive composition of the present invention is preferable because the pattern size has little dependence on the exposure dose. In particular,
The colored photosensitive composition of the present invention is applied onto a substrate or a layer formed of a solid component of the colored photosensitive composition previously formed,
Volatile components are removed from the applied colored photosensitive composition, and the volatile component is removed through a photomask having a pattern size of 100 μm for 200
pattern dimension when exposed in mJ / cm ² (d (20
0)) to the pattern dimension (d (800)) when exposed at 800 mJ / cm ² (d (800) / d (2
A composition in which 00)) is 1.00 or more and 1.10 or less is preferable. It is preferable for d (800) / d (200) to be 1.00 or more and 1.10 or less because a pattern having a smaller exposure dose dependency of the pattern size can be formed.

After exposure, development is performed. For development, for example, the colored photosensitive composition layer after exposure may be brought into contact with a developing solution, and specifically, the substrate having the colored photosensitive composition layer formed on the surface thereof may be developed. Just soak in. Examples of the developer include sodium carbonate, potassium carbonate,
Examples thereof include aqueous solutions of alkaline compounds such as sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. By the development, the non-irradiated regions of the colored photosensitive composition layer which have not been irradiated with light rays are removed. On the other hand, the light beam irradiation area remains as it is to form a pattern.

After development, the desired pattern can be obtained by washing with water and drying. After drying
You may heat. The pattern tends to be cured by heating and its mechanical strength tends to be improved. When a colored photosensitive composition containing a curing agent is used, the mechanical strength can be further improved. . The heating temperature is usually 180 ° C or higher, preferably 200 ° C or higher,
It is usually 250 ° C or lower.

Further, in order to obtain color filters by forming color pixels or black matrix of other colors, by performing the above operation while changing the color of the colorant, it is possible to sequentially form color pixels or black matrix of each color. Good.

When the colored photosensitive composition of the present invention is used for forming a pixel in which the average transmittance at 400-700 nm of each pixel of the color filter is 45% or more, regardless of the thickness of the pixel, it is highly effective. It is preferable because the sensitivity tends to have little dependency on the exposure amount. In particular, when the colored photosensitive composition of the present invention is used for producing a reflective color filter, it tends to have a small exposure dose dependency, which is preferable. The color filter thus obtained includes a pattern,
A suitable liquid crystal display device can be obtained by using the color filter.

[0035]

The embodiments of the present invention have been described above, but the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. Not limited. The scope of the present invention is defined by the claims, and includes the meaning equivalent to the description of the claims and all modifications within the scope. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The following components were mixed to obtain a red colored photosensitive composition. The unit is parts by mass. (A) CI Pigment Red 209 39.3 parts CI Pigment Yellow 138 0.3 parts (B) Binder resin (methacrylic acid / benzyl methacrylate = 27/73, weight average molecular weight = 22,000) 50 Parts (C) dipentaerythritol hexaacrylate 50 parts (D) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 8 parts 4,4′-bis (diethylamino) benzophenone 8 Part (E) 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1, 3,2] Dioxaphosphepine 0.48 parts (F) Propylene glycol monomethyl ether acetate 723 parts Dispersant as an additive 1.7 parts

The obtained colored photosensitive composition was applied onto a glass substrate (Corning # 7059) by a spin coater, and then the coating film was prebaked at 100 ° C. for 3 minutes and dried. Then, with respect to this dried coating film, through a photomask for forming a 100 μm line-and-space pattern, 200 mJ / cm 2 respectively with an ultra-high pressure mercury lamp.
After exposure at ² and 800 mJ / cm ^2, it is immersed in a developing solution (aqueous solution containing 0.05% of potassium hydroxide and 0.2% of sodium butylnaphthalene sulfonate in terms of mass fraction) for development. After washing with water, post-baking was performed at 220 ° C. for 20 minutes to obtain a red image. The thickness of the obtained image was 1.0 μm, and the average transmittance in the range of 400 to 700 nm was 68.0%. 100 μm of this red pixel
When the line width of the line pattern was measured by SEM,
200mJ / cm ² in 104μm, in 800mJ / cm ² 10
At 6 μm, (d (800) / d (200)) is 1.02
It was found that the line width dependence due to the difference in exposure dose was extremely small.

Example 2 The following components were mixed to obtain a red colored photosensitive composition. (A) CI Pigment Red 209 36.9 parts CI Pigment Yellow 138 0.3 parts (B) Binder resin (methacrylic acid / benzyl methacrylate = 27/73, weight average molecular weight = 22,000) 50 Parts (C) dipentaerythritol hexaacrylate 50 parts (D) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 6 parts (E) bis (2,4-di- t-butylphenyl) pentaerythritol diphosphite 0.48 parts (F) propylene glycol monomethyl ether acetate 723 parts dispersant as an additive 1.7 parts

An image was obtained from the obtained colored photosensitive composition in the same manner as in Example 1. The thickness of the obtained image was 1.1 μm, and the average transmittance at 400-700 nm was 69.2%. When the line width of the 100 μm line pattern of the red pixel was measured by SEM, 2
MJ / cm ² in 107Myuemu, in 800 mJ / cm ² 115
In μm, (d (800) / d (200)) was 1.07, and it was found that the line width dependence due to the difference in exposure amount was very small.

Comparative Example 1 The following components were mixed to obtain a blue colored photosensitive composition. (A) CI Pigment Blue 15: 6 14 parts (B) Binder resin (methacrylic acid / benzyl methacrylate = 30/70, weight average molecular weight = 23,000) 50 parts (C) Dipentaerythritol hexaacrylate 50 parts (D) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 12 parts 2,4-diethylthioxanthone 4 parts (E) propylene glycol monomethyl ether acetate 642 parts Dispersed as an additive Agent 0.6 parts

An image was obtained from the obtained colored photosensitive composition in the same manner as in Example 1. The thickness of the obtained image was 1.1 μm, and the average transmittance at 400-700 nm was 55.6%. 100 μm of each pixel obtained
When the line width of the line pattern was measured by SEM,
It was 109 μm at 200 mJ / cm ² , but 800 mJ / c
At m ² , line thickening occurred so as not to be resolved, and the influence of the difference in exposure amount on the pattern size was very large.

Comparative Example 2 The following components were mixed to obtain a red colored photosensitive composition. (A) CI Pigment Red 209 36.9 parts CI Pigment Yellow 138 0.3 parts (B) Binder resin (methacrylic acid / benzyl methacrylate = 30/70, weight average molecular weight = 25,000) 50 Parts (C) dipentaerythritol hexaacrylate 50 parts (D) 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one 6 parts (D) 2,4-diethylthioxanthone 3 parts (E) Propylene glycol monomethyl ether acetate 723 parts Dispersant as an additive 1.7 parts

An image was obtained from the obtained colored photosensitive composition in the same manner as in Example 1. The thickness of the obtained image was 1.0 μm, and the average transmittance thereof at 400-700 nm was 70.0%. 100 μm of each pixel obtained
When the line width of the line pattern was measured by SEM,
It was 109 μm at 200 mJ / cm ² , but 800 mJ / c
At m ² , line thickening occurred so as not to be resolved, and the influence of the difference in exposure amount on the pattern size was very large.

According to the colored photosensitive composition of the present invention, it is possible to form a pattern having a high sensitivity and a small exposure dose dependency of the pattern size.

Claims (7)

[Claims] 1. A colorant (A), a binder polymer (B), a photopolymerizable compound (C), a photopolymerization initiator (D),
A colored photosensitive composition comprising (E) a solvent and (F) a phosphorus-based antioxidant. 2. The (F) phosphorus-based antioxidant is 6- [3-
(3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine and The colored photosensitive composition according to claim 1, which is at least one selected from the group consisting of bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite. 3. The content of (F) phosphorus-based antioxidant is
(D) The content of the photopolymerization initiator is 0.
It is 1% or more and 30% or less, The colored photosensitive composition of Claim 1 or 2. 4. A colored photosensitive composition is applied onto a substrate or a layer formed of a solid component of the colored photosensitive composition previously formed, and volatile components are removed from the applied colored photosensitive composition. , 200m through a photomask with a line width of 100 μm
The line width when exposed at 800 mJ / cm ² to the line width (d (200)) when exposed at J / cm ² (d (80
0)) ratio (d (800) / d (200)) is 1.00
The colored photosensitive composition according to any one of claims 1 to 3, which is 1 to 10 inclusive. 5. A layer comprising the colored photosensitive composition according to any one of claims 1 to 4 is applied onto a substrate or a layer comprising the solid content of the already formed colored photosensitive composition, and applied. A method for forming a colored pattern, which comprises removing a volatile component from a colored photosensitive composition, exposing the layer through a photomask, and developing the layer. 6. A color filter manufactured by the method of claim 5. 7. A liquid crystal display device including the color filter according to claim 6.