JPH04194941A - Colored picture forming material and formation of colored picture - Google Patents

Abstract

PURPOSE:To obtain a material excellent in heat resistance which can form colored picture images by combining a copolymer of (meth)acrylic acid and vinyl monomers, photopolymerizable monomers, photopolymn. initiator, epoxy compd. having epoxy group in the molecule, epoxy hardening agent and pigment. CONSTITUTION:The material to form colored picture images consists of a combination of copolymers of (meth)acrylic acid and vinyl monomers, photopolymerizable monomers, photopolymn. initiator, epoxy compd. having at least two epoxy groups in the molecule, epoxy hardening agent and pigment. The copolymer is, for example, copolymer of acrylic acid and/or methacrylic acid and other vinyl monomers. Thereby, colored picture images excellent in heat resistance can be formed, which improves heat resistance of a color filter used for a liquid display element, solid-state image pickup device, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to colored image forming materials and methods for forming colored images. More specifically, the present invention relates to a light-transmissive colored image forming material such as a color filter, and a method for forming a colored image.

[Conventional technology] Conventionally, color filters for liquid crystal display devices and solid-state image sensors are made by forming patterns using water-soluble natural polymers such as gelatin and casein, and then dyeing them in red, green, and blue. It is created by repeating each colored image (staining method).

[Problems to be Solved by the Invention] The color filter created by this dyeing method has a problem of poor heat resistance because it uses a natural polymer on the layer to be dyed and a dye as a pigment.

Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have developed a material for forming a colored image, such as a color filter, which has excellent light transmittance and heat resistance, and a colored image. We have found a method for forming this, and have arrived at the present invention. That is, the present invention is constituted by the following colored image forming materials (I), (II), (I) and colored image forming methods (Z-1) and (Z-2).

Colored image forming material (I): JT polymer of (meth)acrylic acid and vinyl monomer (A-1), photopolymerizable monomer (B), photopolymerization initiator (C), in molecule 1. A colored image-forming material comprising a combination of an Evoquin compound (D) having at least two epoxy groups, an epoxy curing agent (E) and a pigment (F).

Colored image forming material (n): Reaction product of copolymer (A-1) with vinyl (meth)acrylate monomer and glycidyl (meth)acrylate (A-2), photopolymerizable monomer 1. A colored image-forming material comprising a compound (B), a photopolymerization initiator (C), and a pigment (F).

Colored image-forming material (III): reaction product of a copolymer of (meth)acrylic acid and vinyl monomer with glycidyl (meth)acrylate (A-2), photopolymerizable monomer (B),
A photopolymerization initiator (C), an epoxy compound (D) having at least two epoxy groups in the molecule, an epoxy curing agent (E)
) and a pigment (F) in combination.

Colored image forming method (Z-1): Colored image forming material (I
) or (III) on a substrate, irradiating only a predetermined portion with active energy rays, removing uncured portions by developing with an alkaline aqueous solution, and then heat-treating the colored image. Formation method.

Colored image forming method (Z-2): Colored image forming material (n
) is applied onto a substrate, irradiated with active energy rays only at predetermined areas, then the uncured portions are removed by development treatment with an alkaline aqueous solution, and if necessary, irradiated with active energy rays and/or heat treated. A method for forming a colored image.

In the present invention, examples of the copolymer (A-1) include copolymers of acrylic acid and/or methacrylic acid and one or two other vinyl monomers. Specific examples of other vinyl monomers include esters of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, n-butyl acrylate, methacrylic acid). -n-butyl, isobutyl methacrylate, t-butyl methacrylate, benzyl acrylate-1, benzyl methacrylate, hydroxyethyl methacrylate, phenyl methacrylate, tetrafluoropropyl acrylate, etc.); vinyl group-containing aromatic compounds (styrene , p-hydroxystyrene, p-acetoxystyrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene, etc.); amide compounds (N-methylolacrylamide, N-methylolmethacrylamide, acrylamide, methacrylamide, etc.); and acrylonitrile is simple. Among these, acrylic acid or methacrylic acid esters and vinyl group-containing aromatic compounds are preferred from the viewpoint of controlling developability.

From the viewpoint of solubility in an alkaline aqueous solution, the copolymer (A-1) preferably has a molar content of carboxyl groups derived from acrylic acid or methacrylic acid of 10 to 90%, and the weight of the copolymer The average molecule (1) is preferably from 000 to 500,000, more preferably from 2,000 to 100,000 in terms of polystyrene.

Specific examples of preferred copolymers (A-1) are expressed by combinations of copolymer components: acrylic acid/isobutyl methacrylate copolymer, acrylic acid/isobutyl methacrylate copolymer, acrylic acid/benzyl methacrylate copolymer. Acrylate copolymer, methacrylic acid/α-methylstyrene copolymer, acrylic acid/methyl methacrylate/benzyl acrylate copolymer, methacrylic acid/benzyl methacrylate/n-butyl acrylate copolymer, acrylic acid/
Ethyl methacrylate/n-butyl acrylate copolymer, acrylic acid/methyl methacrylate/α-methylstyrene copolymer, methacrylic acid/ethyl acrylate/α-methylstyrene copolymer, acrylic acid/ethyl acrylate /benzyl acrylate-1/α-methylstyrene copolymer.

Specific examples of preferable reactants (A-2) are expressed by combinations of structural units: acrylic acid-benzyl acrylate copolymer/glycidyl methacrylate (epoxy equivalent/acid equivalent ratio = 0.2 to 1.05); Acrylic acid-(methacrylic acid-〇-butyl) copolymer/glycidyl acrylate-1 (epoxy equivalent/acid equivalent ratio = 0.2~
1.05), methacrylic acid-(α-methylstyrene) copolymer/glycidyl methacrylate (epoxy equivalent M/acid equivalent ratio = 0.2-1.05), acrylic acid-methyl methacrylate-benzyl acrylate copolymer /glycidyl methacrylate (epoxy equivalent/acid equivalent ratio = 0.2-1
．． 05), methacrylic acid-ethyl acrylate-(α-methylstyrene) copolymer/glycidyl acrylate (epoxy equivalent/acid equivalent ratio = 0.2 to 1.05).

To illustrate the method for producing the reaction product (A-2), the copolymer (
A-1) and glycidyl methacrylate and/or glycidyl acrylate in an organic solvent in the presence of a catalyst at an epoxy equivalent/acid equivalent ratio of 0.2 to 1.05, preferably 0.
．． By reacting in the range of 3 to 0.95 (A −
2) can be obtained. Examples of the organic solvents mentioned above include ester compounds (ethyl cellosolve acetate, methyl cellosolve acetate, triethylene glycol diacrylate, nonaethylene glycol diacrylate, etc.), ketone compounds (cyclohexanone, methyl isobutyl ketone, etc.), aromatic compounds (toluene, etc.), water, and mixed solvents thereof can be used. In addition, the above-mentioned catalysts include phosphine compounds (rotriphenylphosphine, tricyclohexylphosphine, tri-n-hexylphosphine, tris(4-methylphenyl)phosphine, etc.); quaternary ammonium salt compounds (benzyltrimethylammonium chloride, benzyltriethyl chloride, etc.); ammonium, tetra-n-butylammonium bromide, etc.); tertiary amine compounds (triethylamine, N.

imidazole compounds (2-methylimidazole, 2-ethyl-4-
methylimidazole, 2-phenylimidazole, etc.)
You can use nato. This reaction is usually carried out in the presence of a polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, etc.). In addition, the reaction conditions are usually 60 to +30°
C1 preferably at a reaction temperature of 70 to 120 °C,
The reaction is usually carried out for 0.5 to 30 hours.

In the present invention, the photopolymerizable monomer (B) includes, for example, polyhydric alcohols (+-lyethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, Ester of (meth)acrylic acid with neopentyl glycol, dipentaerythritol, l-lis(2-hydroxyethyl)isocyanuric acid, etc.; monofunctional monomer [monofunctional (meth)acrylic acid ester (2-hydroxy Ethyl methacrylate, 2-hydroxyethyl methacrylate-1, methoxytetraethylene glycol acrylate, butoxyethyl acrylate, butyl acrylate-1
・, benzyl acrylate, phenoxyethyl acrylate, etc.), monofunctional amide compounds (N-methylol acrylamide, N-methylol methacrylamide, acrylamide, methacrylamide, etc.)]; Esterification of triglycidyl isocyanurate and (meth)acrylate Reaction product [triglycidyl isocyanurate/
Acrylic acid (I/2 molar ratio) reactant, triglycidyl isocyanurate/acrylic acid (1/3 molar ratio) reactant, etc.). These monomers CB) can be used alone or in combination of two or more.

In the present invention, as the photopolymerization initiator (C), any initiator that initiates polymerization of an unsaturated compound by active energy rays such as ultraviolet rays, deep ultraviolet rays, electron beams, and visible light can be used. Specific examples of (C) include benzoin or its alkyl ethers (benzoin isobutyl ether, benzoin isopropyl ether, etc.); acetophenones [2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxyacetophenone, 1-
Hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, ■-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-methylethyl-(p-dodecylphenyl)ketone , 1,1.1-trichloromethyl-(p-butylphenyl)ketone, 2-methyl-(4'
-(methylthio)phenyl)-2-morpholino-1-
Propanone, etc.]; Thioxanthones [thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.]: Benzophenones [ Benzophenone, Michler's ketone, di(
p-diethylaminophenyl) ketone, etc.];
Traquinones (2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-
chloroanthraquinone, etc.); dialkylaminobenzoic acid esters (p-dimethylamine ethyl benzoate,
ethyl p-diethylaminobenzoate, etc.); trihalomethyl-8-triazines [2-(4-methoxyphenyl)-4,G-bis(trichloromethyl)-S-)riazine, 2-(4-methoxynaphthyl)- 4,6-bis(trichloromethyl)-S-triazine, 2-(4-ethoxynaphthyl)-4, B-bis(trichloromethyl)-S
-) riazine, 2-ethoxycarbonyl-4-(4-ethoxynaphthyl)-G-trichloromethyl-8-triazine, etc.; acridines [9-phenylacridine,
9-(p-methoxyphenyl)acridine, etc.]; phenazines (9,10-dimethylbenzphenazine, etc.), and the like. These photopolymerization initiators (C) can be used alone or in combination of two or more. Moreover, (C) and a sensitizer may be used together. Examples of the sensitizer include triethanolamine, methylgetanolamine, ethylgetanolamine, 2-(dimethylamine)ethyl methacrylate, 2-(diethylamino)ethyl methacrylate), 2-(dimethylamino)ethyl acrylate, Examples include 2-(diethylamino)ethyl acrylate.

In the present invention, examples of the epoxy compound (D) include glycidyl ester epoxy compounds, glycidyl ether epoxy compounds, alicyclic epoxy compounds, fluorinated epoxy compounds, glycidylamine epoxy compounds, hydantoin epoxy compounds, triglycidyl isocyanurate, etc. It will be done.

Specific examples of glycidyl ester epoxy compounds include:
Examples include hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, 4-methyltetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, dimer acid glycidyl ester, diglycidyl-p-benzoic acid, and the like. Specific examples of glycidyl ester epoxy compounds include 2,2-bis(4-glycidyloxycyclohexyl)propane,
Bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether,
Bisphenol F diglycidyl ether, glycidyl ether of polyhydroxyalkanes, bisphenol S diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, cyclohexane dimetatool diglycidyl Examples include ether. Specific examples of alicyclic epoxy compounds include 2-(3,4-epoxy)cyclohexyl-5,1
-spiro(3,4-epoxy)cyclohexyl-m-dioxane, bis(3,4-epoxy-6-methylcyclohexyl)adipate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3 , 4-epoxy-6-methylcyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4-vinylcyclohexene dioxide, I-(1
' -methyl-1,2-epoxyethyl) -3,4-
Alicyclic epoxy compounds having a cyclohexene oxide group such as epoxy-3-methylcyclohexane; di(7,8-evoquine tritylene glycol di(7,8-
Examples include alicyclic epoxy compounds having a tricyclodecene oxide group such as epoxytricyclo-2',3'-epoxypropyl ether. Specific examples of fluorinated epoxy compounds include bisphenol hexafluoroacetone diglycidyl ether, 1,3-bis(
1-(2,3-epoxypropane)-1-)lifluoromethyl-2.2.2-)lifluoroethyl)benzene, ■,4-bis(1-(2,3-epoxypropane)
-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorovininyl, and the like. Specific examples of glycidylamine epoxy compounds include m-N,N-diglycidylaminophenylglycidyl ether, N,N-diglycidylaniline, N,
N-diglycidyl-. -Toluidine, N, N.

Examples include N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane and diglycidyl tribromoaniline. Specific examples of hydantoin epoquine = 16- compounds include N,N'-diglycidyl-5,5-dimethylhydantoin, I-(2.3-
epoxypropyl') -3- (2- (2,3-epoxypropyloquine)propyl)-5,5-dimethylhydantoin, N. N'-diglycidyl-5-amyl-5-methylhydantoin, N,N'-diglycidyl-5.

Examples include 5-pentamethylenehydantoin.

Among these epoxy compounds (D), preferred are grindyl ester epoxy compounds, glycidyl ether epoxy compounds, and alicyclic epoxy compounds, and particularly preferred are alicyclic epoxy compounds. These epoxy compounds (D) can be used alone or in combination of two or more.

In the present invention, examples of the epoxy curing agent (E) include acid anhydrides, polyamines, polyphenols, imidazole compounds, tertiary amine compounds, dicyandiamide, boron trifluoride-amine complexes, biguanide compounds, organic acid hydrazides, and the like. .

Specific examples of acid anhydrides include aromatic acid anhydrides [phthalic anhydride, trimellidic anhydride, pyromellitic anhydride-17= acid, benzophenonetetracarboxylic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), alicyclic acid anhydrides (methylnadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, chlorendic anhydride, 5 - (2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1
, 2-dicarboxylic anhydride, etc.); aliphatic acid anhydride (dodecylsuccinic anhydride, etc.). Specific examples of polyamines include aromatic polyamines (methaxylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, etc.)
; Alicyclic polyamine [bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 3,9-bis(3-aminopropy/L/)
-2.4,8.10-tetraoxaspiro(5.5)undecane adduct, N-aminoethylpiperazine, isophoronediamine, methanediamine); aliphatic polyamines (diethylaminopropylamine, triethylenetetramine) , diethylenetriamine, etc.); polyamide polyamines; and modified compounds of these polyamines (evoquin compound-added polyamines, Michael-added polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-blocked polyamines, ethylene oxide-added polyamines, propylene oxide-added polyamines, etc.) can be mentioned.

Specific examples of polyphenols include phenol novolak, talesol novolac, polyvinylphenol, and the like. Specific examples of imidazole compounds include:
Imidazole compounds [2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl-imidazole, 2-phenylimidazole, l-benzyl-2-methylimidazole, Methylimidazole, ■-Cyanethyl-2-ethyl-4-methylimidazole, l
-cyanoethyl-2-undecylimidazole, 2,4
-diamino-6-(2-methylimidazolyl-(1))
-ethyl-8-triazine, 2,4-diamino-6-(
2-Ethyl-4-methylimidazolyl-(1))-ethyl-8-triazine, 2,4-diamino-6-(2-undecylimidazolyl-(1))-ethyl-8-triazine, 2-phenyl- 4-Methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2-phenyl-4,5-
Dihydroxymethylimidazole, ■-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3-dibenzyl-2-methylimidazolium chloride, etc. C; Carboxylic acid salts of imidazole compounds (1-cyanoethyl-2-undecylimidazolium-trimeritate, I-cyanethyl-2-phenylimidazolium-trimeritate-1.nato); incyanuric acid salts of imidazole compounds ( 2-methylimidazolium-isocyanurate-1, 2-phenylimidazolium-isocyanurate, etc.); salts of imidazole compounds and mono- or polyhydric phenols (salts of 2-methylimidazole and alkylphenols, 2-ethyl-4- salts of methylimidazole and alkylphenols); adducts of imidazole compounds and monoepoxy compounds or epoxy resins (adducts of 2-methylimidazole and bisphenol A diglycidyl ether, 2-methylimidazole and alkylcarboxylic acid glycidyl ethers); adducts, etc.).

Specific examples of tertiary amine compounds include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2-(dimethylaminomethyl)phenol.
, 4.6-) lis(dimethylaminomethyl)phenol. Specific examples of the 3-so boron-amine ♀1) complex include a 3-so boron-monoethylamine complex and a 3-so boron-penzylamine complex. Specific examples of biguanide compounds include O-)
Examples include rilbiguanide and phenylbiguanide. Specific examples of the organic acid hydrazide compound include cono-lyric acid hydrazide, adipic acid hydrazide, isophthalic acid hydrazide, and the like. These epoxy hardeners (E
), preferred are aromatic acid anhydrides, alicyclic acid anhydrides, imidazole compounds and aromatic polyamines. These epoxy curing agents can be used alone or in combination of two or more, and for example, it is also useful to use them as a eutectic mixture.

In the present invention, as the pigment (F), the pigments suitable for forming colored images such as red, green, blue, and black as described above are used.

For forming a red colored image, a red pigment, a mixture of a red pigment and a yellow pigment, etc. are used, and for the purpose of hue adjustment, it is preferable to use a red pigment and a yellow pigment in combination. Specific examples of the red pigment include Pigment Red 9, +23, +55, +68, +77.180 in color index name.
．． 217.220.224, and specific examples of the yellow pigment include Pigment Yellow 20.24.83.93.109.110.117.
125.139.147 and +54. Two or more of these red pigments and yellow pigments can be used in combination. When using a red pigment and a yellow pigment together, the amount of yellow pigment used is 0.5 to the red pigment.
It is preferable to use it in a range of 30% by weight from the viewpoint of hue adjustment.

For forming a green colored image, a green pigment, a mixture of a green pigment and a yellow pigment, etc. are used, and for the purpose of hue adjustment, it is preferable to use a green pigment and a yellow pigment in combination. Specific examples of the green pigment include phthalocyanine pigments (color index names such as Pigment Green 7.36.37), and specific examples of the yellow pigment include color index names such as Pigment, :c o -20,24,83,
93, +09, I 10. , +17, +25.1
39.147.154 is mentioned. Two or more of these green pigments and yellow pigments can be used in combination. When a green pigment and a yellow pigment are used together, the amount of yellow pigment used is 0.5 to 30% by weight relative to the green pigment.
From the viewpoint of hue adjustment, it is preferable to use within this range.

For forming a blue colored image, a blue pigment or a mixture of a blue pigment and a violet pigment is used, and for the purpose of hue adjustment, it is preferable to use a blue pigment and a violet pigment in combination. Specific examples of the blue pigment include phthalonanine pigments (color index names: Pigment Blue 15.15:3, +5:4.
15:G, etc.), anthraquinone pigments (color index names such as Pigment Blue 22, [io, etc.), and specific examples of the purple pigments include color index names such as Pigment Violet 19.23.29.3.
7.50 is mentioned. Two or more of these blue pigments and purple pigments can be used in combination.

When a blue pigment and a violet pigment are used together, the amount of the violet pigment to be used is preferably in the range of 0.5 to 30% of the blue pigment from the viewpoint of hue adjustment.

A black pigment such as carbon blank is used to form a black colored image.

The above-mentioned phthalocyanine pigments include solvent-soluble pigments having substituents such as alkyl groups, alkyloxy groups, alkyloxycarbonyl groups, alkylamido groups, and alkyloxy groups [(1-butyl)4PC-Cus (n
-hekynruoxy)JPC-Cu> etc.] can also be used.

In addition, in the case of color filters used in solid-state image sensors, pigments suitable for forming yellow, magenta, and cyan colored images can be used instead of the red, green, and blue colored images mentioned above. , a pigment suitable for each application is selected.

The colored image-forming material (I) of the present invention comprises the copolymer (A
-1) For 100 parts by weight, the photopolymerizable monomer (B)
usually 20 to 400 parts by weight, preferably 30 to 250 parts by weight, the photopolymerization initiator (C) usually 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, the epoxy compound (
D) is usually 10 to 300 parts by weight, preferably 20 to 25 parts by weight.
0 parts by weight, usually 0.01 to 2 parts of the epoxy curing agent (E)
00 weight L1 part, preferably 0.1 to 150 parts by weight, and the pigment (F) is usually 20 to 300 parts by weight, preferably 30 to 150 parts by weight.
It is preferable to use within the range of 250 parts by weight in order to form a colored image layer with excellent heat resistance, resolution, etc.

The colored image forming material (n) of the present invention comprises the reaction product (A-
2) For 100 parts by weight, the photopolymerizable monomer (B) is usually 20 to 400 parts by weight, preferably 30 to 250 parts by weight, and the photopolymerization initiator (C) is usually 0.1 to 30 parts by weight. It is preferable to use the pigment (F) in an amount of 25 to 20 parts by weight, usually 20 to 250 parts by weight, preferably 30 to 200 parts by weight, for excellent heat resistance and resolution. This is preferable for forming a colored image layer.

The colored image-forming material (III) of the present invention comprises the reaction product (
A-2) For 100 parts by weight, the photopolymerizable monomer (B)
usually 20 to 400 parts by weight, preferably 30 to 250 parts by weight, the photopolymerization initiator (C) usually 0.1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, the epoxy compound (
D) is usually 10 to 300 parts by weight, preferably 20 to 25 parts by weight.
0 parts by weight, usually 0.01 to 2 parts of the epoxy curing agent (E)
00 parts by weight, preferably 0.1-150 parts by weight, and the pigment (F) is usually 20-300 parts by weight, preferably 30-2
It is preferable to use it in a range of 50 parts by weight and 111 parts in order to form a colored image layer with excellent heat resistance, resolution, etc.

The colored image forming materials (I) to (II[) of the present invention include:
If necessary, (G) Pigment dispersant [anionic pigment dispersant (polycarboxylic acid type polymer activator, polysulfonic acid type polymer activator, etc.), nonionic pigment dispersant (polyoxylene ethylene, boriogin propylene, (block polymers, etc.), organic dye derivatives (phthalocyanine, anthraquinone, helylene, quinacridone, etc.), including sulfonamide groups, carbonamide groups, sulfonic acid groups, sulfonic acid bases, carboxyl groups, and hydroxyl groups. (IH silane coupling agents [epoxy foundation silane cups such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.); Ringing agents, vinyl group-containing silane coupling agents such as vinyltrimethoxysilane and γ-metallyloxypropyltrimethoxysilane, amino-based silane coupling agents such as γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Mercapto group-containing silane coupling agents such as silane]; (J) titanate coupling agents (isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryloyl titanate, isopropyl trimethacryloyl titanate, isopropyl), acryloyl titanate-1,
(diisopropylisostearoyl-4-aminobenzoyl titanate, etc.); (K) polysiloxane (polyphenylmethylsiloxane, polyether-modified polylinoxane, etc.); (L) antioxidant [2,G-')-t-butyl-4- Phenolic antioxidants such as methylphenol, phosphorus antioxidants such as tris(2,4-di-t-butylphenyl)phosphite, dilauryl-3,3-
- sulfur-based antioxidants such as thione propionate]; (M) UV absorbers (phenyl salicylate-based UV absorbers, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and anoacrylate-based UV absorbers) , benzoate-based ultraviolet absorbers); (N)
Active agent: Fluorosurfactant (perfluoroalkylsulfonic acid ammonium salt, perfluoroalkylsulfonic acid alkali metal salt, perfluoroalkyl quaternary ammonium iodide, fluorinated alkyl ester, etc.), silicone surfactant, carbonized hydrogen-based surfactants, etc.];
(P) Thermal polymerization inhibitor (Ha=28-irroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, etc.); (Q) Adhesive agent (benzotriazole, 5-
amino-1,3,4-thiadiazole-2-thiol,
(5-mercapto-IH-1,2,4-triazole, etc.); (S) Amine resin (melamine-formaldehyde amine resin, urea resin, benzoguanamine resin, etc.)
etc. can be used together.

The colored image-forming materials (I) and (III) of the present invention may be obtained by dissolving or dispersing all components in a solvent if there is no problem with storage stability. In addition, when it is necessary to improve storage stability, for example, epoxy compound (D)
(1) and (III) are composed of two solutions: a solution containing epoxy curing agent (E) and a solution containing epoxy curing agent (E).

The other components may be blended into either of these two liquids. In this case, it is required that the other components mentioned above be added to the liquid that does not react during storage. If there is no problem in blending it into either solution, a portion of the same component may be blended separately into both solutions. The solvent used in both the one-part and two-part cases is not particularly limited as long as it dissolves or disperses these components and does not react with them. Specific examples of this solvent include esters (ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl acetate, butyl acetate, isobutyl isobutyrate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc.), ethers ( Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, butyl ether, diisoamyl ether, diethylene glycol, ethylene glycol monomethyl ether, etc.), ketones (methyl isobutyl ketone, cyclohexanone, etc.), halogenated hydrocarbons ( 1,2-ethylene dichloride, dichlorobenzene, etc.), and two or more kinds of solvents and mixtures thereof can be used if necessary. The concentrations of (I) and (III) are not particularly limited and are appropriately selected depending on the purpose of use and coating method, but it is usually preferable to use a diluted solution of about 10 to 80% by weight and 1%. (I) and (III) may be further diluted with the solvents exemplified above at the time of use.

The colored image forming material (n) of the present invention is usually one in which all components are dissolved or dispersed in a solvent.

As the solvent, (I) and (III) exemplified above can be used.
Solvents similar to can be used. The concentration of (II) is not particularly limited and is appropriately selected depending on the purpose of use and coating method, but it is usually preferable to use a diluted solution of about 10 to 80% by weight. (n) may be further diluted with the solvent exemplified above at the time of use.

When dissolving or dispersing each component in each of the above (I) to (III), a known dispersing machine can be used, such as a ball mill, a roll mill, a sand mill, an attritor, a daysilver, and other dispersing and mixing equipment. etc. are used.

From the viewpoint of light transmittance of a colored image, the average particle diameter of the pigment during dispersion is preferably at most visible light wavelength (400 to 700 nm), more preferably at most 0.2 μm.

The copolymer (A-]) and the reactant (A-2) containing a dicarboxyl group used in the material of the present invention have properties as an anionic polymeric pigment dispersant. Furthermore, it is also effective to use various pigment dispersants (G) in combination during the dispersion described in section 2.

In the present invention, the substrate includes, for example, a light-transmissive substrate [glass substrate such as white glass (such as Corning 7058 material), soda glass (soda glass), silica-coated soda glass, acrylic resin, polycarbonate resin, polyether sulfone] Examples include a mechanical resin substrate made of resin, a semiconductor substrate having a photoelectric conversion element, and the like. The light-transmitting substrate described above is used as a substrate for a color filter used in a liquid crystal display element, and the light-transmitting substrate or semiconductor substrate described above is used as a substrate for a color filter used in a solid-state image sensor.

Examples of methods for applying the colored image-forming materials of the present invention onto a substrate include spin cord coating, roll coat coating, The coating film thickness is usually 0.2 by bar coater coating, spray coating, printing coating, etc.
Apply to a thickness of ~30 μm.

In the colored image forming method (Z-1) of the present invention, this coating film is subjected to, for example, pattern exposure using a photomask,
By a method such as direct writing by scanning the active energy rays, an exposed area (the predetermined area) and an unexposed area are created, and curing progresses selectively only in the exposed areas. Examples of the active energy rays include ultraviolet rays, far ultraviolet rays, electron beams, and visible light, and as the light source, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a far ultraviolet lamp, a visible light laser, etc. can be used. Unexposed areas should be developed using an aqueous alkaline solution (an aqueous solution of a base such as an alkali metal carbonate such as sodium carbonate, an alkali metal hydroxide such as sodium hydroxide, or an organic alkali such as tetramethylammonium hydroxide). Since it is dissolved and removed, a colored image consisting of a coating film only on the predetermined area can be formed. Next, heat treatment is performed at a temperature of usually 80 to 250°C for usually about 5 minutes to 120 minutes in the same manner as the method exemplified above, and the cured film is further cured by thermal polymerization and crosslinking, thereby forming a colored image. be able to. For the heat treatment, a circulating furnace, a hot plate, an infrared furnace, a far-infrared furnace, etc. can be used.

In the formation method (Z-2), the above-mentioned formation method (Z-
By the same method as in 1), a colored image consisting of a coating film only on the predetermined area is first formed by coating, exposing, and developing operations. After this, if it is necessary to further complete the curing of the colored image, re-irradiation with active energy rays and/or heat treatment as exemplified above may be performed.

In the above formation methods (Z-1) and (Z-2), it is effective to cover the coating film with an oxygen barrier film (polyvinyl alcohol film, etc.) or to perform exposure under a nitrogen atmosphere to accelerate curing. It is. Furthermore, curing may be accelerated by heat treatment during or after exposure.

The colored images thus formed can be combined to form a color filter. To illustrate the method of forming a color filter using a liquid crystal display element, the above-mentioned materials and methods are repeatedly used for each color on a glass substrate to form a colored image of red, green, blue, etc. A method of forming a black colored image as a black matrix in the area where no image is formed between images. After forming a black matrix by etching a thin chromium film or the above-mentioned black colored image, etc., There is a method of forming a colored image.

[Examples] Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 a)y IJ acid/benzyl acrylate-1-(19/8
1 weight ratio) copolymer (weight average molecular weight 23,000,
Carbogisil Fund rate 35 mol%) 35 parts, C, 1, (
Color index) Pigment Red 177 to 37.
After roughly dispersing 7 parts of C.1, 6.3 parts of Pigment Yellow 83 and 240 parts of ethyl cellosolve acetate, the mixture was machine dispersed for 1 hour in a sand mill using steel beads. 7 parts of 2-hydroquine ethyl acrylate and 8 parts of trimethylolpropane triacrylate were added to 300 parts of this fine dispersion.
parts, 2 parts of 1-hydroxycyclohexyl phenyl ketone, 5 parts of I,G-hexanediol diglyphzyl ether, 25 parts of bis(3,4-epoxycyclohegycylmethyl)adipate, 2 parts of 2-phenylimidazole, and ethyl A red colored image forming material of the present invention was obtained by mixing 150 parts of cellosolve acetate. Glass substrate "Second"
After spin-coding the colored image forming abrasive material mentioned above, 80'
C. for 10 minutes to obtain a coating film with a coating thickness of 2.0 μm. Then, through a negative mask, a super-pressure mercury lamp was used for 5
After 00 mj/cm2 exposure, spray development using 1% carbon dioxide solution at 30°C for 1 minute, spray rinsing with water for 1 minute, and remove only the exposed areas on the substrate. -36 = A color image was formed. This was heated at 150°C for 30 minutes to form a colored image. The obtained colored image is placed in the air 2
Table 1 shows the results of evaluating heat resistance based on tape peeling adhesion and chemical resistance after beta testing at 00°C for 1 hour.

Example 2 Acrylic acid/methyl methacrylate/benzyl acrylate
) (22/2215G weight ratio) copolymer (weight average molecular weight 30,000, carboquine group content 35 mol%
) 37 parts, C, 1, Pigment Green 3G 37.7
After roughly dispersing 6.3 parts of Pigment Yellow 83 and 240 parts of ethyl cellosolve acetate, the mixture was dispersed in a sand mill using steel beads for 1 hour. Add 300 parts of this fine dispersion to 2-hydroquine ethyl acrylate).
・5 parts, 10 parts of pentaerythritol triacrylate, 2-methyl-[:4'-(methylthio)phenyl]
-2-morpholino■-propanone 2 parts, 3,4-epoxycyclohequinylmethyl-3,4-epoxycyclohexanecarboxylate 30 parts, 1-benzyl-2-methylimidazole 2 parts, γ-glycidoxypropyltri A green colored image forming material of the present invention was obtained by mixing 2 parts of methoxysilane and 150 parts of ethyl cellosolve acetate. Table 1 shows the results of evaluating this in the same manner as in Example 1.
Shown below.

Example 3 35 parts of the copolymer used in Example 1, 37.7 parts of C,1, Pigment Blue 15, 6.3 parts of C,1, Pigment Violet 23, and ethyl cellosolve acetate.
After dispersing 1.240 parts in 4 parts, the mixture was dispersed in a sand mill using a steel piece for 1 hour. To 300 parts of this fine dispersion were added 5 parts of trimethylolpropane triacrylate, 10 parts of pentaerythritol triacrylate, 2 parts of 2-methyl-[4'-(methylthio)phenyl-2-morpholino-1-propuff, and hexahydrophthalic acid. 30 parts of diglycine ester, 7 parts of l-limellitic anhydride,
30 parts of diethylene glycol dimethyl ether and 1-130 parts of ethyl cellosolve acetate were mixed to obtain the blue colored image forming material of the present invention. This was evaluated in the same manner as in Example] and the results are shown in Table 1.

Example 4 Methacrylic acid/ethyl acrylate/α-methylstyrene (23/+7/80 weight ratio) copolymer (weight average molecular weight 20,000, carboxyl base content 28 mol%)
), 35 parts of carbon black, and 240 parts of ethyl cellosolve acetate were coarsely dispersed, and then finely dispersed for 1 hour in a sand mill using steel beads. This fine dispersion liquid 3
00 parts, 5 parts of 2-hydroxyethyl acrylate, 5 parts of trimethylolpropane triacrylate, 10 parts of l-liglycidyl isocyanurate/acrylic acid (molar ratio of ]/3) reactant, 2-(4-methoxyphenyl)- 4
, G-bis(trichloromethyl)-S-) riazine 2 parts, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarpoxylate 30 parts, 2-phenylimidazole 2 parts, γ-glycidoxypropyl A black colored image-forming material of the present invention was obtained by mixing 2 parts of trimethoxysilane and 150 parts of ethyl cellosolve acetate. The above-mentioned colored image-forming material was spin-coded onto a glass substrate, and then beta-coated at 80°C for 10 minutes to obtain a coating film with a coating thickness of 2.0 μm. Then, 500mj/cm” was applied using an ultra-high pressure mercury lamp through a negative mask.
After exposure, the film was exposed to light at 80° C. for 10 minutes, and then developed, rinsed, and heated in the same manner as in Example 1 to form a colored image. This was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 50 parts of acrylic acid/benzyl acrylate (45/55 weight ratio) copolymer (weight average molecular weight 15,000, carboxyl group content 65 mol%), 27.4 parts of glycidyl methacrylate, 0.0 parts of hydroquinone monomethyl ether. 2 parts, benzyltriethylammonium chloride 0.
Dissolve 3 parts in 115 parts of ethyl cellosolve acetate,
The reaction was carried out at 100°C for 10 hours, and a reactant solution (A-
2a) was obtained. 89 parts of this reactant solution (A-2a), C
,I.

After coarsely dispersing 25.7 parts of Pigment Red +77, 4.3 parts of C.1, Pigment Yellow 83, and 140 parts of ethyl cellosolve acetate, the mixture was finely dispersed in a sand mill using a steel piece for 1 hour. To 245 parts of this fine dispersion, 10 parts of 2-hydroxyethyl acrylate, 12 parts of pentaerythritol triacrylate, 2-methyl-
[2 parts of 4'-(methylthio)phenyl-2-morpholino-1-propanone and 70 parts of ethyl cellosolve acetate were mixed to obtain a red colored image-forming material of the present invention. After spin-coding the colored image-forming material on a glass substrate, it was baked at 80'C for 10 minutes to obtain a coating film with a coating thickness of 2.0 μm. Next, after exposing the substrate to 500 mj/cm2 using an ultra-high pressure mercury lamp through a negative mask, spray development was performed at 30°C for 1 minute using a 1% sodium carbonate aqueous solution, and spray rinsing was performed using water for 1 minute. A colored image was formed only in the exposed area. Table 1 shows the results of evaluating heat resistance based on tape peeling adhesion and chemical resistance after baking the obtained colored image in air at 200° C. for 1 hour.

Example 6 86 parts of the copolymer used in Example 5, 25.7 parts of C,1, Pigment Green 36, 4.3 parts of C,1, Pigment Yellow 83, and ethyl cellosolve acetate 1
After roughly dispersing 40 parts, fine dispersion was performed for 1 hour using a sand mill using steel beads. To 245 parts of this fine dispersion were added 6 parts of 2-hydroxyethyl acrylate, 510 parts of trimethylolpropane triacrylate trisritol triacrylate, and 2-(4-methquinphenyl)-4,G-bis(trichloromethyl).
-S-) 2 parts of riazine, 2 parts of γ-glycidoxypropyltrimethoxysilane and 1 part of ethyl cellosolve acetate
- 70 parts were mixed to obtain a green colored image forming material of the present invention. Table 1 shows the results of evaluating this in the same manner as in Example 1.
Shown below.

Example 7 50 parts of methacrylic acid/ethyl acrylate/α-methylstyrene (52/G/42 weight ratio) copolymer (weight average molecular weight 15,000, carboxyl group content 59 mol%), 22 parts of glycidyl acrylate. 9 parts of hydroquinone monomethyl ether, 0.2 parts of benzyltriethylammonium chloride, and 0.3 parts of benzyltriethylammonium chloride were dissolved in 110 parts of ethyl cellosolve acetate) and reacted at IoooC for 10 hours to obtain a non-volatile content of 42% by weight and an acid value of 3G. Om g K
An anti-forgetfulness solution (A-2b) of OH/g was obtained. 90 parts of this reactant solution (A-2b), 25.7 parts of C,1, Pigment Blue 15, 4.3 parts of C,1, Pigment Violet 23, and ethyl cellosolve acetate-1-1.
After roughly dispersing 40 parts, the mixture was machine dispersed for 1 hour in a sand mill using steel beads. To 245 parts of this fine dispersion, 7 parts of 2-hydroxyethyl acrylate, 10 parts of l-thumethylorpropane triacrylate, 4 parts of pentaerythritol triacrylate, 2 parts of 1-hydroxycyclohexylphenyl ketone, and γ-glycidoxy 2 parts propyltrimethoxysilane and 70 parts ethyl cellosolve acetate
A blue colored image forming material of the present invention was obtained by mixing the two parts. This was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 8 88 parts of the copolymer used in Example 7, 37.7 parts of C,1, Pigment Red +77, 8.3 parts of C,1, Pigment Yellow 83, and ethyl cellosolve acetate 1
After roughly dispersing 85 parts, the mixture was dispersed in a sand mill using steel beads for 1 hour. To 300 parts of this fine dispersion were added: 5 parts of 2-hydroquine ethyl acrylate, 510 parts of trimethylolpropane triacrylate, 2-methyl-[
2 parts of 4'-(methylthio)phenyl]-2-morpholino-1-propanone, 30 parts of hexahydrophthalic acid diglycidyl ester, 2 parts of I-benzyl-2-methylimidazole, 2 parts of γ-glycidoxypropyltrimethoxine oran and 150 parts of ethyl cellosolve acetate) were mixed to obtain a red colored image forming material of the present invention. This was evaluated in the same manner as in Example 1, and the results are shown in Table -■.

Example 9 90 parts of the copolymer used in Example 5, 37.7 parts of C,1, Pigment Green 36, C,1, Pigment x
6.3 parts of o-83 and ethyl cellosolve acetate
After roughly dispersing 1 to 185 parts, the mixture was machine dispersed for 1 hour in a sand mill using steel beads. To 300 parts of this fine dispersion, 5 parts of trimethylolpropane triacrylate, 4 parts of pentaerythritol triacrylate, 2 parts of 2,2-dimethoxy-2-phenylacetophenone, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate rate 30 parts, trimellidic anhydride 7 parts,
A green colored image forming material of the present invention was obtained by mixing 30 parts of diethylene glycol dimethyl ether and 130 parts of ethyl cellosolve acetate. This was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 10 After roughly dispersing 88 parts of the copolymer used in Example 7, 37.7 parts of C,1, Pigment Blue 15, 6.3 parts of C,1, Pigment Violet 23, and 185 parts of ethyl cellosolve acetate. The mixture was dispersed in a sand mill using steel beads for 1 hour. Add 2- to 300 parts of this fine dispersion.
5 parts of hydroxyethyl acrylate, 5 parts of trimethylolpropane triacrylate, 5 parts of pentaerythritol triacrylate, 2 parts of 1-hydroxycyclohexylphenyl ketone, 30 parts of bis(3,4-epoxycyclohexylmethyl)adipate, 2-phenylimidazole 2 parts, 2 parts of γ-glyndoxypropyltrimethquinone, and ethyl cellosolve acetate) 15
0 parts were mixed to obtain a blue colored image forming material of the present invention. This was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 11 86 parts of the copolymer used in Example 5, 44 parts of carbon black, and 185 parts of ethyl cellosolve acetate were roughly dispersed and then machine dispersed for 1 hour in a sand mill using steel beads. To 300 parts of this fine dispersion, 5 parts of 2-hydroxyethyl acrylate, 10 parts of 2-(4-methoxyphenyl)-4
, G-bis(trichloromethyl)-S-) riazine 2 parts, 30 parts 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane rupoxylate, 7 parts trimellidic anhydride, γ-glycidoxypropyltrimethoxysilane 2 parts of diethylene glycol dimethyl ether and 130 parts of ethyl cellosolve acetate were mixed to obtain a black colored image forming material of the present invention. This was evaluated in the same manner as in Example 4, and the results are shown in Table 1.

Comparative Example 1 A gelatin aqueous solution containing ammonium dichromate was spin-coded on a glass substrate, and then beta-coated at 80°C for 10 minutes to obtain a coating film with a coating thickness of 2.0 μm.

Next, 700 ml of heat was applied using an ultra-high pressure mercury lamp through a negative mask.
m j / cm", and then developed with warm water to form a dyed layer only on the exposed area on the glass substrate. This was coated with Suminol Fast or Red G [manufactured by Sumitomo Chemical Co., Ltd.] 2g1 It was immersed in a dye bath consisting of 3 g of acetic acid and 100 g of water at 60°C for 15 minutes, washed with water, and further dried at +20°C for 30 minutes to obtain a red colored image.

The heat resistance of this colored image was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Margin below this page) =47- Table-1 (Note) Evaluation method: Tape peeling; J I S ll-0202 chemical resistance; a-35% hydrochloric acid aqueous solution, 40°C x 15 minutes b-10
%NaOH aqueous solution, appearance change after 15 minutes immersion at 40℃
○: No change ×: Peeling [Effects of the invention] The method of the present invention using the colored image forming material of the present invention has the following effects:
It exhibits remarkable hardening as follows.

(1) A colored image with excellent heat resistance can be formed,
The heat resistance of color filters used in liquid crystal display devices, solid-state image sensors, etc. can be significantly improved.

(2) Colored images with excellent chemical resistance and adhesion can be formed, and the chemical resistance and adhesion of color filters used in liquid crystal display elements, solid-state image sensors, etc. can be significantly improved.

(3) Pigments can be finely dispersed. Therefore, compared to the use of dyes, not only can colored images be obtained that are free from fading and yellowing due to heat and/or light, but also colored images with excellent light transmittance can be obtained.

(4) The composition obtained by removing the pigment from the colored image forming material of the present invention is a resin composition that has excellent properties such as heat resistance, chemical resistance, and adhesion, and has excellent properties such as protection of color filters, flattening, etc. It can be used as a protective film material for the purpose of From this, the colored pixels of the color filter and the protective film can be formed using similar cured resin materials.
It is possible to prevent deterioration of adhesion on the laminated surface, such as peeling caused by differences in the thermal expansion coefficients of each material, which occurs during the sealing process of the surrounding parts (e.g., vapor deposition of an ITO film).

(5) After forming two or more colored images by repeating the exposure and development operations, heat treatment is performed to simplify the process of creating images consisting of two or more colored images such as color filters. be able to.

-50=

Claims (1)

[Claims] 1. Copolymer of (meth)acrylic acid and vinyl monomer (
A-1), photopolymerizable monomer (B), photoinitiator (C)
, an epoxy compound (D) having at least two epoxy groups in the molecule, an epoxy curing agent (E), and a pigment (F)
A colored image forming material characterized by being formed by combining the following. 2. Copolymer of (meth)acrylic acid and vinyl monomer (
A-1) and glycidyl (meth)acrylate reaction product (A-2), photopolymerizable monomer (B), photopolymerization initiator (C
) and a pigment (F). 3. Reaction product of copolymer of (meth)acrylic acid and vinyl monomer and glycidyl (meth)acrylate (A-2)
, a photopolymerizable monomer (B), a photopolymerization initiator (C), an epoxy compound having at least two epoxy groups in the molecule (
D), an epoxy curing agent (E), and a pigment (F) in combination. 4. After coating the colored image forming material according to claim 1 or 3 on a substrate, irradiating only a predetermined portion with active energy rays, removing the uncured portion by developing with an alkaline aqueous solution, and then heat-treating. A method for forming a colored image, characterized in that: 5. After coating the colored image forming material according to claim 2 on a substrate, only predetermined areas are irradiated with active energy rays, and uncured areas are removed by development treatment with an alkaline aqueous solution, and if necessary, active energy rays are applied. 1. A method for forming a colored image, comprising irradiation and/or heat treatment.