JP2002296778A - Color photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color photosensitive composition which can form color pixels or the like excellent in solvent resistance even when the composition contains a coloring agent (A) with high concentration. SOLUTION: The color photosensitive composition contains a coloring agent (A), binder polymers (B) having monomer units having oxoethane structures, photopolymerizable compounds (C) and a photopolymerization initiator (D).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a colored photosensitive composition.

[0002]

2. Description of the Related Art Colored photosensitive compositions (color resists)
Is a colored photosensitive composition (resist) containing a colorant, and is useful as a raw material for forming a colored pattern (5) constituting a color filter (6). Here, the color filter is, for example,
This filter is incorporated in a color liquid crystal display device and used for colorizing a display image, or incorporated in a color solid-state imaging device and used for obtaining a color image. The coloring pattern includes, for example, a color pixel (5R, 5G, 5B), a black matrix (5B
M). The color pixels consist of a colored transparent layer. The black matrix blocks light. These color pixels and the black matrix are usually formed on a substrate (2) to form a color filter (6) (FIG. 1). Here, the color pixels (5R, 5G, 5R) are transparent, and the transmitted light is colored in the color of each color pixel.
The black matrix (5BM) is a layer that blocks light.

As a colored photosensitive composition, for example, a composition containing a colorant (A), a binder polymer (B), a photopolymerizable compound (C) and a photopolymerization initiator (D) is known. Alkali-soluble resins are usually used as the binder polymer (B). The colored pattern (5) formed using the colored photosensitive composition preferably has a small thickness. In order to obtain a colored pattern that is sufficiently colored even if the thickness is small, a colored photosensitive composition containing the coloring agent (A) at a high concentration may be used.

However, the conventional binder polymer (B)
When a coloring agent (A) is contained at a high concentration in a colored photosensitive composition containing, there is a problem that the solvent resistance of a colored pattern formed using the colored photosensitive composition is reduced.

[0005]

The present inventors have been keen to develop a colored photosensitive composition capable of forming a colored pattern having excellent solvent resistance even if the coloring agent (A) is contained at a high concentration. As a result of the study, the colored photosensitive composition obtained by using a binder polymer containing a monomer unit having an oxetane skeleton as the binder polymer (B) has high resistance even when the coloring agent (A) is contained at a high concentration. The present inventors have found that a colored pattern having excellent solvent properties can be formed, and have reached the present invention.

[0006]

That is, the present invention provides a colorant (A), a binder polymer (B) containing a monomer unit having an oxetane skeleton, a photopolymerizable compound (C), and a photopolymerization initiator (D). ) Is provided.

[0007]

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 that is an organic substance or an inorganic colorant that is an inorganic substance. .
The organic colorant may be a pigment, a dye, or a natural pigment. Inorganic colorants include metal oxides, metal complex salts, and inorganic salts of barium sulfate (enrichment pigment)
And other inorganic pigments. Among the coloring agents,
Organic colorants and organic pigments are preferably used in terms of excellent heat resistance and color development.

Specific examples of organic pigments and inorganic pigments include a color index (The Society of Dyers and C
olourists), which are classified as Pigment. Specifically, C.I. I. Pigment Yellow 1, C.I. I. Pigment Yellow 3, C.I.
I. Pigment Yellow 12, C.I. 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 2
4, C.I. I. Pigment Yellow 31, C.I. I. Pigment yellow 53, C.I. I. Pigment Yellow 83,
C. I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I.
I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment Yellow 117,
C. I. Pigment yellow 125, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 13
7, C.I. I. Pigment yellow 138, C.I. I. Pigment Yellow 139, C.I. I. Pigment Yellow 1
47, 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. I. Pigment Yellow 173,

C. I. Pigment Orange 13, C.I.
I. Pigment Orange 31, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I.
Pigment Orange 40, C.I. I. Pigment Orange 42, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 5
5, C.I. I. Pigment Orange 59, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64,
C. I. Pigment Orange 65, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 73,

C. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I. I. Pigment Red 10
5, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 144,
C. 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 177, C.I. I. Pigment Red 180, C.I. I.
Pigment Red 192, C.I. I. Pigment Red 2
09, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 22
4, C.I. I. Pigment Red 242, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264,
C. I. Pigment Red 265,

C. I. Pigment Blue 15, C.I. I.
Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I.
I. Pigment Blue 60,

C. I. Pigment Violet 1, C.I.
I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 2
9, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 38,

C. I. Pigment Green 7, C.I. I.
Pigment Green 36, 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 the like. These organic pigments and inorganic pigments may be used alone or in combination of two or more.

Among these organic pigments and inorganic pigments,
Organic pigments, if necessary, rosin treatment, surface treatment using a pigment derivative into which an acidic or basic group has been introduced,
A graft treatment to the pigment surface with a polymer compound or the like, an atomization treatment by a sulfuric acid atomization method or the like, or a washing treatment with an organic solvent or water for removing impurities may be performed.

The content of the coloring agent (A) is usually 5% by mass to 60% by mass based on the total solid content of the colored photosensitive composition.
% By mass, preferably 10% by mass or more and 50% by mass or less, more preferably 20% by mass or more, particularly 3% by mass.
It is suitable when the content is 0% by mass or more. When an organic pigment is used, the amount of the organic pigment used is usually at least 50% by mass, preferably at least 55% by mass, based on the total amount of the colorant (A).

The binder polymer (B) is a polymer containing a monomer unit having an oxetane skeleton. Here, as the monomer having an oxetane skeleton, for example,
Formula (I-1) And an oxetane skeleton represented by the formula (I-2): [Wherein, R ¹ has the same meaning as described above. And a compound having a carbon-carbon double bond represented by the formula (I) [Wherein, R ¹ represents a hydrogen atom or a methyl group, X represents a methylene group or an ethylene group, and R ² represents a methyl group or an ethyl group. And the like.

The monomer includes, for example, 3-methyl-
3-methacryloxymethyloxetane, 3-methyl-
3-acryloxymethyloxetane, 3-ethyl-3-
Methacryloxymethyl oxetane, 3-ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, 3 -Ethyl-3-acryloxyethyl oxetane and the like.

The monomer unit having an oxetane skeleton in the binder polymer is a unit derived from the monomer having the oxetane skeleton, but the monomer unit having the oxetane skeleton may be of one type. Or two or more types.

The binder polymer is preferably a copolymer of a monomer having an oxetane skeleton and another monomer. Other monomers include monomers that can be copolymerized with monomers having an oxetane skeleton, such as unsaturated monocarboxylic acids and unsaturated dicarboxylic acids having at least one carboxyl group in the molecule. Examples thereof include saturated carboxylic acids, and specific examples 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.

Other monomers include, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl. Unsaturated carboxylic acid ester compounds such as (meth) acrylate and benzyl (meth) acrylate; unsaturated carboxylic acid aminoalkyl ester compounds such as aminoethyl acrylate; unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate;
Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl propionate, and vinyl cyanide compounds such as (meth) acrylonitrile and α-chloroacrylonitrile are also included. These monomers are monomers having an oxetane skeleton or monomers copolymerizable with the above-mentioned unsaturated carboxylic acid, and are used alone or in combination of two or more.

Examples of the copolymer include 3-ethyl-3-methacryloxymethyloxetane / benzyl methacrylate / methacrylic acid copolymer and 3-ethyl-3-methacrylate.
Methacryloxymethyl oxetane / benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl-
3-methacryloxymethyl oxetane / methyl methacrylate / methacrylic acid copolymer, 3-ethyl-3-methacryloxymethyl oxetane / methyl methacrylate /
Examples include methacrylic acid / styrene copolymer.

The content of the monomer unit having an oxetane skeleton in the copolymer is usually 3% by mass or more by mass fraction.
It is preferably at least 5% by mass, usually at most 95% by mass,
Preferably it is 90 mass% or less. The content of the unsaturated carboxylic acid unit is usually at least 5% by mass, preferably at least 10% by mass, and usually at most 50% by mass, preferably at most 40% by mass in terms of mass fraction.

The binder polymer has a weight average molecular weight (a value measured by gel permeation chromatography as a value in terms of polystyrene) of 5,000.
It is preferably in the range of 0 to 400,000, more preferably 10,000 to 300,000.
The range is as follows. The content of the binder polymer (B) is usually 5% by mass or more, preferably 20% by mass or more, and more preferably 90% by mass or less, based on the solid content of the colored photosensitive resin composition. Is 70% by mass or less.

The photopolymerizable compound (C) is a compound which can be polymerized by an active radical, an acid or the like generated from the photopolymerization initiator (D) upon irradiation with light. Compounds having an unsaturated bond are exemplified. The compound may be a monofunctional photopolymerizable compound or a bifunctional or trifunctional or higher polyfunctional photopolymerizable compound.

As the monofunctional photopolymerizable compound, for example,
Nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like can be mentioned. As the bifunctional photopolymerizable compound, for example, 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- Methylpentanediol di (meth) acrylate and the like can be mentioned. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The photopolymerizable compounds may be used alone or in combination of two or more. However, a bifunctional or higher polyfunctional photopolymerizable compound is preferably used, and when two or more photopolymerizable compounds are used. It is preferable to use one or more polyfunctional photopolymerizable compounds. The content of the photopolymerizable compound (C) is usually 0.1 part by mass or more and 70 parts by mass or less, preferably 1 part by mass, per 100 parts by mass of the total amount of the binder polymer (B) and the photopolymerizable compound (C). It is not less than 60 parts by mass and not more than parts by mass.

Examples of the photopolymerization initiator (D) include an active radical generator that generates an active radical when irradiated with light, and an acid generator that generates an acid. Examples of the active radical generator include: Acetophenone compounds,
Examples include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based 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-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl- 2
-Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1-
[4- (1-methylvinyl) phenyl] propane-1-
ON oligomers and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether. As the benzophenone-based compound, for example, benzophenone, o-
Methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-
Trimethylbenzophenone and the like. Examples of the thioxanthone-based compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone,
4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the triazine compound include, 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, methyl phenylglyoxylate, titanocene compounds and the like can also be used. As the active radical generator, a commercially available product can be used. As a commercially available photopolymerization initiator, for example,
Trade name "Irgacure-907" (acetophenone-based photopolymerization initiator, manufactured by Ciba Specialty Chemicals) and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate,
Onium salts such as acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitro Benzyl tosylate, benzoin tosylate and the like can be mentioned. Further, among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine-based compound can be used as the acid generator. These photopolymerization initiators can be used alone or in combination of two or more.

The colored photosensitive composition of the present invention may contain a photopolymerization initiation aid. The photopolymerization initiation aid is a compound used in combination with the photopolymerization initiator to promote the polymerization of the photopolymerizable compound (C) 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, and 2-aminobenzoate. Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, , 4'-bis (ethylmethylamino) benzophenone and the like.

Examples of the alkoxyanthracene-based compound include, for example, 9,10-dimethoxyanthracene,
Ethyl-9,10-dimethoxyanthracene, 9,10
-Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene and the like. Commercially available photopolymerization initiation aids can be used, and examples of commercially available photopolymerization initiation aids include “EAB-F” (trade name, manufactured by Hodogaya Chemical Industry Co., Ltd.).

When the photopolymerization initiator is used, its content is usually 10 mol or less, preferably 0.01 mol or more and 5 mol or less per 1 mol of the photopolymerization initiator.

The total amount of the photopolymerization initiator (D) and the photopolymerization initiator is usually 3 parts by mass or more based on 100 parts by mass of the total amount of the binder polymer (B) and the photopolymerizable compound (C). It is preferably at least 5 parts by mass, usually at most 30 parts by mass, preferably at most 25 parts by mass.

The colored photosensitive composition of the present invention may be diluted with a solvent (E). As the solvent, the same solvents as those used in ordinary colored photosensitive compositions are used, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Alkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Alkylene glycol alkyl ether acetates such as tyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; anisole, phenetole and methylanisole; Aromatic aliphatic ethers, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2
-Ketones such as pentanone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate,
Esters such as methyl 3-methoxypropionate and ethyl lactate; and cyclic esters such as γ-butyrolactone. These solvents can be used alone or in combination of two or more, and the content of the solvent in the colored photosensitive composition diluted with the solvent is usually 50% by mass or more, preferably 60% by mass, in terms of mass fraction. It is used in an amount of not less than 90% by mass, usually not more than 90% by mass, preferably not more than 85% by mass.

The colored photosensitive composition of the present invention may contain an additive (F). Examples of the additive include a filler, a polymer compound other than the binder polymer (A), a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, an organic acid, an organic amino compound, and a curing agent. And the like.

Examples of the filler include glass and alumina.

Examples of the high molecular compound include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate and the like.

Examples of the surfactant include a nonionic surfactant, a cationic surfactant, an anionic surfactant and the like.

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. .

As the antioxidant, for example, 4,4'-
Thiobis (6-t-butyl-3-methylphenol),
2,6-di-t-butyl-4-methylphenol and the like.

As the ultraviolet absorber, for example, 2- (2
-Hydroxy-3-t-butyl-5-methylphenyl)
Benzotriazoles such as -5-chlorobenzotriazole, benzophenones such as 2-hydroxy-4-octyloxybenzophenone, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxy Benzoate type such as benzoate is exemplified.

Examples of the anti-agglomeration agent include sodium polyacrylate.

Examples of the organic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, 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 and camphoronic acid, benzoic acid, toluic acid, cuminic acid, hemelitic acid,
Examples 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, melophanic 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, dii-propylamine, di-n-butylamine, dii
Dibutylamines such as -butylamine, sdiec-butylamine, dit-butylamine, di-n-pentylamine and di-n-hexylamine; monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine; dicyclohexylamine Such as dicycloalkylamines, dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine,
Methyl di-n-propylamine, ethyl di-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 and 6-amino-1-hexanol, 4-amino-1-
Monocycloalkanolamines such as cyclohexanol, diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, dii-butanolamine, di-n-pentanolamine dialkanolamines, di-n- Dialkanolamines such as hexanolamine, dicycloalkanolamines such as di (4-cyclohexanol) amine,
Triethanolamine, tri-n-propanolamine,
Trialkanolamines such as tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine and tri-n-hexanolamine, and 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,
Amino-cycloalkanediols such as 4-amino-1,3-cyclohexanediol; amino-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol; 1-aminocyclohexanone methanol; Amino-containing cycloalkane methanols 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, 4-aminocyclohexanecarboxylic acid, aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, p-n-propylaniline, p-i -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 for curing the color pixels and the like by a heat treatment after development to improve the mechanical strength. As the curing agent, for example, a compound capable of reacting with the oxetane skeleton or carboxyl group of the binder polymer by heating to crosslink the binder polymer can be mentioned, and by curing the binder polymer, a color pixel or the like is cured. Further, a compound which can be polymerized by heating alone may be used, and the color pixel or the like is cured by polymerizing alone. Examples of the compound include an epoxy compound and an oxetane compound.

Examples of the epoxy compound include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, and other aromatic epoxy resins. , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, epoxy resins such as epoxidized oils, brominated derivatives of these epoxy resins, other than epoxy resins and their brominated derivatives Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co)
Epoxidized polymer, epoxidized (co) isoprene polymer, (co) glycidyl (meth) acrylate
Examples thereof include polymers and triglycidyl isocyanurate.

Examples of the oxetane compound include carbonate bis oxetane, xylylene bis oxetane,
Adipate bisoxetane, terephthalate bisoxetane, bisoxetane cyclohexanedicarboxylate and the like can be mentioned.

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

Examples of the polycarboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,
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, itaconic acid, hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexa Hydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid,
Alicyclic polycarboxylic acids such as cyclopentanetetracarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid;

Examples of the polycarboxylic anhydrides include aromatic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride. Polycarboxylic anhydrides, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride,
Aliphatic polycarboxylic anhydrides such as maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride; 2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, anhydrous hymic Examples include alicyclic polycarboxylic acid anhydrides such as acid and nadic anhydride, and ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitate acid and glycerin tristrimellitate anhydride.

As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents may be used. Examples of the epoxy resin curing agent include “ADEKA HARDNER EH-700” (manufactured by Asahi Denka Kogyo Co., Ltd.), “RICACID HH” (manufactured by Nippon Rika Co., Ltd.), and “M
H-700 "(manufactured by Shin Nippon Rika Co., Ltd.).
The curing agents can be used alone or in combination of two or more.

The colored photosensitive composition of the present invention is prepared, for example, by mixing a colorant (A), a binder polymer (B), a photopolymerizable compound (C) and a photopolymerization initiator (D) in a solvent (E). When the additive (F) is contained, in the solvent (E), the coloring agent (A), the binder polymer (B), the photopolymerizable compound (C), and the photopolymerization initiator (D) And the additive (F).

In order to form a colored pattern (5) using the colored photosensitive composition of the present invention, for example, a layer (1) composed of the colored photosensitive composition of the present invention is formed on a substrate (2). (FIG. 2 (a)), the layer (1) may be exposed to light (4) via a photomask (3) and exposed (FIG. 2 (b)), and then developed.

Examples of the substrate (2) include substrates having a flat surface such as a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. The substrate is a chemical treatment with a chemical such as a silane coupling agent, a plasma treatment, an ion plating treatment,
A pretreatment such as a sputtering treatment, a gas phase reaction treatment, or a vacuum deposition treatment may be performed. When a silicon substrate or the like is used as a substrate, a charge-coupled device (CCD), a thin film transistor (TFT, Th
in Film Transistor) may be formed. In order to form the layer (1) composed of the colored photosensitive composition on the substrate (2), for example, a colored photosensitive resin composition diluted with a solvent is spin-coated (spin-coated) or cast-coated. It may be applied to the substrate by a usual method such as a roll coating method, a slit & spin coating method, and then the solvent may be volatilized. In order to remove the solvent, for example, heating may be performed on a hot plate.

Next, light beam (4) is irradiated and exposed.
As the light beam (4), g-line (wavelength 436 nm), i
Ultraviolet rays such as a line (wavelength 365 nm) are used. The light beam is applied through a photomask (3). Here, the photomask is, for example, a glass plate (31) provided with a light-shielding layer (32) for shielding the light beam.
The light beam (4) is shielded by the light shielding layer (32). The portion of the glass plate (31) where no light-shielding layer is provided is a light-transmitting portion (33) that transmits light, and the colored photosensitive composition layer (2) is colored according to the pattern of the light-transmitting portion (33).
Is exposed. The irradiation amount of the light beam is determined based on the type and content of the binder polymer (A) used, the color and content of the pigment (B),
It is appropriately selected according to the type and content of the photopolymerizable compound (C) and the type and content of the photopolymerization initiator (D).

After the exposure, development is performed. For development, for example, the colored photosensitive composition layer after exposure may be immersed in a developer. As the developer, for example, an aqueous solution of an alkaline compound such as sodium carbonate, sodium hydroxide, potassium hydroxide, potassium carbonate, and tetramethylammonium hydroxide is used. By the development, the non-light-irradiated area (11) of the colored photosensitive composition layer which is not irradiated with light is removed. On the other hand, the light-irradiated area (12) irradiated with the light remains to constitute a color pixel or the like (5).

After development, the desired colored pattern (5) can be obtained usually by washing with water and drying. However, after drying, heat treatment may be performed. By performing the heat treatment, the formed color pixels and the like are hardened, and the mechanical strength is improved. It is preferable to use a coloring photosensitive composition containing a curing agent, because heat treatment can further improve the mechanical strength of a color pixel or the like. The heating temperature is usually 180 ° C. or higher, preferably about 200 ° C. or higher and 250 ° C. or lower.

The colored pattern (5) thus obtained is obtained by irradiating the colored photosensitive composition of the present invention with light, and has excellent solvent resistance.

In order to obtain a color filter by forming a color pixel of another color and a black matrix, the above operation is performed while changing the color of the colorant (A). May be formed.

[0064]

According to the colored photosensitive composition of the present invention, a colored pattern having excellent solvent resistance can be formed even if the coloring agent (A) is contained at a high concentration.

[0065]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 (Production of Binder Polymer A1) Four-necked flask equipped with a stirrer, a condenser, and a thermometer (the content was 500 cm
³ ) In addition, methacrylic acid (25.8 g), benzyl methacrylate (105.7 g), 3-ethyl-3-methacryloxymethyl oxetane (18.4 g), propylene glycol monomethyl ether acetate (278.5).
g) and azobisisobutyronitrile (3.6) were added, and the mixture was stirred for 5 hours while maintaining the internal temperature at 65 to 75 ° C to obtain a binder polymer A1. This polymer A1
Is a copolymer of methacrylic acid, benzyl methacrylate, and 3-ethyl-3-methacryloxymethyloxetane, and was polymerized at a charge ratio.

(Production of Colored Photosensitive Composition) The components shown in Table 1 were mixed in the composition shown in Table 1 to obtain a colored photosensitive composition.

(Formation of Blue Pixel) After applying the colored photosensitive composition obtained above on the surface of a glass substrate (“# 7059”, manufactured by Corning Incorporated) (2) by spin coating, the composition was heated at 100 ° C. for 3 hours. After drying for a minute, a colored photosensitive composition layer (1) was formed. After cooling, the formed colored photosensitive composition layer (1) was applied to the i-line (wavelength 3) through a photomask (3).
65 nm). An ultra-high pressure mercury lamp was used as an i-ray light source, and the irradiation light amount was 150 mJ / cm ² . Next, a developer (0.05% potassium hydroxide and 0.2% sodium butylnaphthalenesulfonate by mass fraction)
(Aqueous solution containing each), developed, washed with pure water, and then heated at 230 ° C. for 20 minutes to obtain a blue pixel (5).
Was formed. The resulting blue pixels were in the desired pattern.

[0069]

[Table 1] Pigment C.I. I. Pigment Blue 15: 6 4.75 parts by mass Binder polymer A1 5.00 parts by mass Photopolymerizable compound dipentantaerythritol hexaacrylate 5.86 parts by mass (manufactured by Nippon Kayaku Co., Ltd., "KAYARAD DPHA") Photopolymerization initiator "Irgacure-907" 1.30 parts by mass (manufactured by Ciba Specialty Chemicals) "KAYACURE DETX-S" 0.65 parts by mass (manufactured by Nippon Kayaku Co., Ltd.) Additive Pigment dispersant 1.44 parts by mass Solvent Monomethyl ether acetate 81 parts by mass ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

(Evaluation) Solvent resistance A colored layer was formed over the entire surface of the glass plate (2) by operating in the same manner as described above except that the i-ray was irradiated without passing through a photomask. On top of this colored layer, N-methyl-2-
Pyrrolidone (NMP) (2 cm ³ ) was dropped, left at 40 ° C. for 30 minutes, the surface was washed with NMP (2 cm ³ ), and the washing was visually observed. No color was observed in the washing. After the colored layer after washing with NMP was washed with water and dried, the surface of the colored layer was observed with a reflection optical microscope and found to be smooth. 2. Peeling test According to the method described in JIS K5400, the colored layer was 1 m thick.
When 100 pieces were cross-cut in a square pattern of m □, and a peeling test was performed using a cellophane tape from above, no peeling of the colored layer from the substrate was observed.

Comparative Example 1 (Preparation of Binder Polymer A2) The same operation as in Example 1 was carried out except that the amount of benzyl methacrylate used was 124.1 g and 3-ethyl-3-methacryloxymethyloxetane was not used. A binder polymer A2 was obtained. The binder polymer A2 was a copolymer of methacrylic acid and benzyl methacrylate, and was polymerized at a ratio according to the charge ratio.

(Production of Colored Photosensitive Composition and Formation of Blue Pixel) The procedure of Example 1 was repeated, except that 5.0 parts by mass of the binder polymer A2 obtained above was used instead of the binder polymer A1. A colored photosensitive composition was obtained, and a blue pixel was formed.

(Evaluation) A glass plate (2) was prepared in the same manner as in Example 1 except that the colored photosensitive composition obtained in Example 1 was used instead of the colored photosensitive composition obtained in Example 1. A colored layer was formed over the entire surface and evaluated in the same manner as in Example 1. When the washing liquid was visually observed in the solvent resistance test, coloring was observed in the washing liquid. After the colored layer after washing with NMP was washed with water and dried, the surface of the colored layer was observed with a reflection optical microscope, and fine irregularities were observed on the surface. In the peeling test, no peeling from the substrate was observed.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a structure of a color filter.

FIG. 2 is a schematic view showing a step of forming a color pixel using a colored photosensitive composition.

[Explanation of symbols]

1: colored photosensitive composition layer 2: substrate 3: photomask 31: glass plate 32: light-shielding layer 33: light-transmitting portion 4: light beam 5: colored pattern (color pixel or black matrix)

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA04 AA06 AB09 AB13 AC01 AD01 BC13 BC42 BD25 CA00 CC11 2H048 BA45 BA47 BA48 BB02 BB42 4J100 AB02Q AB03Q AL03Q AL08P AL09Q AL10Q AM02Q BC58P CA03 CA04 DA61 EA01 JA37 JA38

Claims (8)

[Claims] 1. A composition comprising a colorant (A), a binder polymer (B) containing a monomer unit having an oxetane skeleton, a photopolymerizable compound (C) and a photopolymerization initiator (D). Colored photosensitive composition. 2. The colored photosensitive composition according to claim 1, wherein the binder polymer (B) is a copolymer of a monomer having an oxetane skeleton and another monomer. 3. The colored photosensitive composition according to claim 2, wherein the content of the monomer unit having an oxetane skeleton in the copolymer is not less than 3% by mass and not more than 95% by mass. 4. The content of the binder polymer (B) is 5% by mass based on the solid content of the colored photosensitive composition.
4. The colored photosensitive composition according to claim 1, wherein the content is at least 90% by mass. 5. 5. The content of the coloring agent (A) is from 5% by mass to 60% by mass with respect to the solid content of the colored photosensitive composition.
The colored photosensitive composition according to claim 1, wherein the colored photosensitive composition is as follows. 6. A layer comprising the colored photosensitive composition according to any one of claims 1 to 5 is formed on a substrate, and the layer is exposed to a light beam through a photomask, exposed, and then developed. A method for producing a color filter, comprising: 7. A colored pattern, wherein the colored photosensitive composition according to claim 2 is irradiated with a light beam. 8. A color filter comprising the colored pattern according to claim 7.