JPH04180064A - Formation of color filter protecting material and protecting layer - Google Patents

Abstract

PURPOSE:To form a color filter protecting layer by subjecting a coating film formed by coating with a specified compsn. having a prescribed mixing ratio to prescribed exposure, hardening and development and removing the unexposed part by dissolution. CONSTITUTION:About 30-250pts.wt. photopolymerizable monomer such as polyol and about 0.5-20pts.wt. photopolymn. initiator which initiates the polymn. of an unsatd. compd. under active energy beams are added to 100pts.wt. copolymer of acrylic acid with a vinyl monomer and they are uniformly mixed in a solvent. A coating film is formed by coating with the resulting compsn. and subjected to prescribed exposure, hardening and development and the unexposed part is removed by dissolution to form a surface protecting layer only at a prescribed part. By the conventional development, a color filter protecting layer having superior heat resistance and resolution can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present RFiA relates to a surface protection material for a color filter and a method for forming a surface protection layer for a color filter.

[Prior Art] Color filters for liquid crystal display elements and the like are usually manufactured by dyeing methods, dye dispersion methods, pigment dispersion methods, printing methods, electrodeposition methods, etc., but generally for the purpose of surface protection and/or Alternatively, a protective layer is formed on the red, green, and blue colored layers for the purpose of resisting dyeing of pigeon houses manufactured using the dyeing method.

Conventionally, acrylic epoxy resins have been known as this surface protection material (for example, JP-A-Sho Eil=292GO
Publication No. 4).

[Problems to be Solved by the Invention] In the production of color filters for the above-mentioned liquid crystal display elements, color filters are used to improve the adhesion of the sealing part and the reliability of the connection between the transparent conductive material and the circuit board part in the mounting terminal part. There is a need to remove all but a portion of the protective film and form the transparent conductive material directly on the glass surface without using the protective film. The above-mentioned protective material requires dry etching to remove unnecessary portions of the protective film, but there are problems with process adaptation, such as increased equipment size and reduced productivity.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors found that unnecessary parts can be removed by irradiation with active energy rays and development after coating, and the material is heat resistant and resistant. The present invention was achieved by discovering a method for forming a surface protective material and a surface protective layer for color filters that are excellent in various properties required for this application, such as chemical properties and transparency. That is, the present invention provides the following surface protection materials (I) to (■) and the method for forming a surface protection layer (2).
-1) and (Z -2).

Surface protection material (I): A combination of a copolymer (A-1) of (meth)acrylic acid and a vinyl monomer, a photopolymerizable monomer (B), and a photopolymerization initiator (C). A surface protection material for color filters featuring:

Surface protection material (■): Copolymer of (meth)acrylic acid and vinyl monomer (A-1), photopolymerizable monomer (B), photopolymerization initiator (C), epoxy in the molecule At least 2 groups
Epoxy compound (D) and epoxy curing agent (
A surface protection material for a color filter, characterized by being made by combining E).

Surface protection material (III): reaction product of copolymer (A-1) of (meth)acrylic acid and vinyl monomer and glycidyl (meth)acrylate (A-2), photopolymerizable monomer (
A surface protection material for a color filter, comprising a combination of B) and a photopolymerization initiator (C).

Surface protection material (rV): reaction product of copolymer of (meth)acrylic acid and vinyl monomer and glycidyl (meth)acrylate (A-2), photopolymerizable monomer (B), photopolymerization A surface protection material for a color filter, characterized by a combination of an initiator (C), an epoxy compound (D) having at least two epoxy groups in the molecule, and an epoxy curing agent (E).

Method for forming a surface protective layer (Z-1): After coating the surface protective material (I) or (DI) on a color filter, active energy rays are irradiated only on predetermined areas, and then the surface protective material (I) or (DI) is coated on a color filter, and then the surface protective material (I) or (DI) is irradiated with active energy rays only at predetermined areas. A method for forming a surface protective layer of a color filter, which comprises removing a cured portion and, if necessary, irradiating with active energy rays and/or heat-treating.

Formation method of surface protective layer (Z-1): After applying the surface protective material (It) or (mV) on the color filter, active energy rays are irradiated only on predetermined areas, and then the surface protective material (It) or (mV) is applied with an alkaline aqueous solution. A method for forming a surface protective layer of a color filter, which comprises removing uncured portions by development treatment and then heat treatment.

In the present invention, examples of the copolymer (A-1) include copolymers of acrylic acid and/or methacrylic acid and one or more 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, 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-methylol acrylamide, N-methylol methacrylamide, acrylamide, methacrylamide, etc.); and acrylonitrile. Among these, from the point of view of developing property control,
Acrylic acid or methacrylic acid esters and vinyl group-containing aromatic compounds are preferred.

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 molecular weight is preferably 1,000 to 500,000, more preferably 2,000 to 100,000 in terms of polystyrene.

Specific examples of preferred copolymers (A-1) include acrylic acid/isobutyl methacrylate copolymer, acrylic acid/n-butyl methacrylate copolymer, acrylic acid/benzyl acrylate copolymer, and 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/α-
Examples include methylstyrene copolymers.

A specific example of a preferable reactant (A-2) is acrylic acid-benzyl acrylate copolymer/glycidyl methacrylate (epoxy equivalent/acid equivalent ratio=0.
2 to 1.05), acrylic acid-(n-butyl methacrylate) copolymer/glycidyl acrylate (epoxy equivalent/acid equivalent ratio = 0.2 to 1.05), methacrylic acid-
(α-methylstyrene) copolymer/glycidyl methacrylate (epoxy equivalent/acid equivalent ratio = 0.2 to 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 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, xylene, etc.). etc.), water, and mixed solvents thereof can be used. In addition, as the above-mentioned catalyst, phosphine compounds [such as triphenylphosphine, tricyclohexylphosphine, tri-n-hexylphosphine, and tris(4-methylphenyl)phosphine]; quaternary ammonium salts (
Benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetra-n-butylammonium bromide, etc.): Tertiary amine compounds (triethylamine,
NlN-dimethylbenzylamine, N,N-dimethylaniline, diazabicyclooctane, etc.); imidazole compounds (2-methylimidazole, 2-ethyl-4
-methylimidazole, 2-phenylimidazole, etc.). This reaction is usually carried out in the presence of a polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, etc.). The reaction conditions are usually 60 to 130°C, preferably 70 to 120°C, and 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 (triethylene glycol, tetraethylene glycol, ethylene glycol, propylene glycol, trimethylolpropane, pentaerythritol, neopentyl glycol, dipenta Erythritol, tris(2-hydroxyethyl)incyanuric acid, etc.) and (meth)acrylic acid ester; monofunctional monomer [monofunctional (meth)acrylic acid ester (2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate) , methoxytetraethylene glycol acrylate, cyclohexyl acrylate, butoxyethyl acrylate, butyl acrylate, benzyl acrylate, phenoxyethyl acrylate, etc.), monofunctional amide compounds (N-methylolacrylamide, N-methylolmethacrylamide, acrylamide, methacrylamide, etc.) Esterification reaction product of triglycidyl isocyanurate and (meth)acrylate [triglycidyl isocyanurate/acrylic acid (l/
2 molar ratio) reactant, and triglycidyl isocyanurate/acrylic acid (1/3 molar ratio) reactant. These monomers (B) 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, l-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone,! -Hydroxy-1-methylethyl-(p-dodecylphenyl)ketone, 1,1,1-)lichloromethyl-(p-butylphenyl)ketone, 2-methyl-
(4'-(methylthio)phenyl)-2-morpholino-1-propanone, etc.]; Thioxanthone [thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-
Conibenzophenones such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisofurovirthioxanthone [benzophenone, Michler ketone,
di(p-diethylaminophenyl)ketone, etc.; anthraquinones (2-methylanthraquinone, 2-dithylanthraquinone, 2-t-butylanthraquinone, ]-
(chloroanthraquinone, etc.); dialkylaminobenzoic acid esters (ethyl p-dimethylaminobenzoate,
ethyl p-diethylaminobenzoate, etc.); trihalomethyl-5-) liazine [2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-) riazine, 2-(4-methoxynaphthyl) -4, &-bis(
trichloromethyl)-8-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-
S-) riazine, 2-ethoxycarbonyl-4-(4-
ethoxynaphthyl)-6-)lichloromethyl-8-)riazine, etc.]; Acridines [9-phenylacridine, 9-(p-methoxyphenyl)acridine, etc.] Coniphenazines (9,10-dimethylbenzphenazine, etc.), etc. It will be done. These photoinitiators (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-(dimethylamino)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. .

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 ether epoxy compounds include 2,2-bis(4-glycidyloxycyclohexyl)propane,
Bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether,
Bisphenol F diglycidyl ether, polyhydroxyalkane glycidyl ether, bisphenol S diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, cyclohexane dimetatool diglycidyl ether Examples include. 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, 1-(1'
Alicyclic epoxy compounds having a cyclohexene oxide group such as -methyl-1,2-epoxyethyl) -3,4-epoxy-3-methylcyclohexane; di(7
Examples include alicyclic epoxy compounds having a tricyclodecene oxide group such as , 8-epoxy 7-tritylene glycol di(7,8-epoxy tridichloro 2', 3'-epoxypropyl ether).Fluorinated epoxy compounds Specific examples include bisphenol hexafluoroacetone diglycidyl ether, l,3-bis(1-(
2,3-epoxypropane)-1-trifluoromethyl-2,2,2-)lifluoroethyl)benzene, 1.4
-bis(1-(2,3-epoxypropane)-1-trifluoromethyl-2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)
Examples include octafluorovininyl. Specific examples of glycidylamine epoxy compounds include m-N, N-
diglycidylaminophenyl glycidyl ether, N,
N-diglycidylaniline, N, N-diglycidyl-〇-toluidine, N, N.

N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, diglycidyl tribromoaniline, and the like. Specific examples of hydantoin epoxy compounds include N,N'-diglycidyl-5,5-dimethylhydantoin, 1-(2,3-epoxyprobyl)-
3-(2-(2,3-epoxypropyloxy)propyl)-5,5-dimethylhydantoin, N,N'-diglycidyl-5-amyl-5-methylhydantoin, N
, N'-diglycidyl-5°5-pentamethylenehydantoin, and the like.

Among these epoxy compounds (D), preferred are glycidyl ester epoxy compounds, glycidyl ether epoxy compounds, alicyclic epoxy compounds, and triglycidyl isocyanurate.

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, benzophenone tetracarboxylic 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 anhydrides (dodecylsuccinic anhydride, etc.). Specific examples of polyamines include aromatic polyamines (methaxylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, etc.); alicyclic polyamines [bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)methane, etc.]; -3-methylcyclohexyl)methane, 3
,9-bis(3-aminopropyl)-2,4,8,10
- tetraoxaspiro(5,5) undecane adduct,
N-aminoethylpiperazine, isophorone diamine, menthene diamine, etc.; aliphatic polyamines (diethylaminopropylamine, triethylenetetramine, diethylene triamine, etc.); polyamide polyamines; and modified compounds of these polyamines (epoxy compound addition polyamines, Michael addition polyamines, etc.); polyamines, Mannich-added polyamines, thiourea-added polyamines, ketone-blocked polyamines, ethylene oxide-added polyamines, propylene oxide-added polyamines, etc.).

Specific examples of polyphenols include phenol novolak, cresol novolak, 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, l-cyanoethyl-2 -methylimidazole, l-cyanoethyl-2-ethyl-4-methylimidazole, l
-cyanoethyl-2-undecylimidazole, 2.4
-diamino-6-(2-methylimidazolyl-(1))
-ethyl-8-) riazine, 2,4-diamino-〇-(
2-ethyl-4-methylimidazolyl-(1) ) −
Ethyl-8-)riazine, 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, l-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, l-dodecyl-2-methyl-3-benzylimidazolium chloride, l,3-dibenzyl-2
-methylimidazo1noum chloride, etc.]; Carboxylate salts of imidazole compounds (l-cyanoethyl-2-undecylimidazolium-trimelitate, l-cyanoethyl-2-phenylimidazolium-trimelitate, etc.); Incyanurate salts of imidazole compounds (2-methylimidazolium-trimelitate, etc.); -methylimidazolium-isocyanurate, 2-phenylimidazolium-isocyanurate, etc.); Salts of imidazole compounds and mono- or polyhydric phenols (salts of 2-methylimidazole, alkylphenols, and alkylphenols, etc.); Imidazole compounds and monohydric phenols Examples thereof include epoxy compounds or adducts with epoxy resins (adducts of 2-methylimidazole and bisphenol A diglycidyl ether, adducts of 2-methylimidazole and alkyl carboxylic acid glycidyl ether, etc.). Specific examples of the tertiary amine compound include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, and 2,4.6-tris(dimethylaminomethyl)phenol. Specific examples of the boron trifluoride-amine complex include boron trifluoride-monoethylamine complex, boron trifluoride-benzylamine complex, and the like. Specific examples of biguanide compounds include 0-tolyl biguanide and phenyl biguanide. Specific examples of organic acid hydrazide compounds include succinic acid hydrazide, adipic acid hydrazide, and isophthalic acid hydrazide. Among these epoxy curing agents (E), preferred are aromatic acid anhydrides,
These are 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.

The surface protection material (I) of the present invention comprises the copolymer (A-1) 1
00 parts by weight, the photopolymerizable monomer (B) is usually 20 parts by weight.
~400 parts by weight, preferably 30 to 250 parts by weight, and using the photopolymerization initiator (C) in the range of usually 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight improves heat resistance,
This is preferable for forming a surface protective layer with excellent resolution.

The surface protection material (II) of the present invention comprises the copolymer (A-1)
The amount of the photopolymerizable monomer (B) is usually 2 to 100 parts by weight.
0 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) usually Using the epoxy curing agent (E) in an amount of usually 0.01 to 200 parts by weight, preferably 0.1 to 150 parts by weight improves heat resistance, This is preferable for forming a surface protective layer with excellent resolution.

The surface protection material (III) of the present invention comprises the reactant (A-2)
300 parts by weight, the photopolymerizable monomer (B) is usually 20 to 400 parts by weight, preferably 30 to 250 parts by weight,
Use of the photopolymerization initiator (C) in a range of usually o, i to 30 parts by weight, preferably 0.5 to 20 parts by weight is effective in forming a surface protective layer with excellent heat resistance, resolution, etc. preferable.

The surface protection material (IV) of the present invention comprises the reactant (A-2)
The amount of the photopolymerizable monomer (B) is usually 2 to 300 parts by weight.
0 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) usually Using the epoxy curing agent (E) in an amount of 10 to 300 parts by weight, preferably 20 to 250 parts by weight, usually 0.01 to 200 parts by weight, preferably 0.1 to 150 parts by weight, improves heat resistance, This is preferable for forming a surface protective layer with excellent resolution.

The surface protection materials (I) to (IV) of the present invention may contain (F) a silane coupling agent [γ-glycidoxyprobyltrimethoxysilane, β-(3°4-epoxycyclohexyl)ethyltrimethoxysilane, Epoxy group-containing silane coupling agents such as methoxysilane, vinyl group-containing silane coupling agents such as vinyltrimethoxysilane, γ-methallyloxypropyltrimethoxysilane, amino group-containing silane cups such as γ-aminopropyltrimethoxysilane (G) Titanate coupling agents (isopropyl triisostearoyl titanate, isopropyl isostearoyl diacryloyl titanate, isopropyl trimethacryloyl titanate, isopropyl trimethacryloyl titanate, etc.); Acryloyl titanate, diisopropylisostearoyl
4-aminobenzoyl titanate, etc.'): (H)
Polysiloxane (polyphenylmethylsiloxane, polyether-modified polysiloxane, etc.); (J) Antioxidants [phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol, tris(2,4- G
(K) Ultraviolet absorber (
Phenyl salicylate UV absorbers, benzophenone UV absorbers, benzotriazole UV absorbers, cyanoacrylate UV absorbers, benzoate UV absorbers, etc.); (L) Active agents [fluorosurfactants (
perfluoroalkylsulfonic acid ammonium salts, perfluoroalkylsulfonic acid alkali metal salts, perfluoroalkyl quaternary ammonium iodides, fluorinated alkyl esters, etc.), silicone surfactants, hydrocarbon surfactants, etc.]; (M ) Thermal polymerization inhibitors (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, etc.);
(N) Adhesive agent (benzotriazole, 5-amino-1,3,4-thiadiazole-2-thiol, 5-
mercapto-1)i-1,2,4-)riazole, etc.)
(P) A polymeric binder that is soluble in an aqueous alkali solution and insoluble in water (at least one unsaturated carboxylic acid selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and maleic anhydride); Copolymers of acids or acid anhydrides with vinyl monomers, etc.); amino resins (melamine-formaldehyde amino resins, urea resins, benzoguanamine resins, etc.) can be used in combination.

The surface protection materials (I) to (mV) of the present invention are used by uniformly mixing the respective constituent components in a solvent.

This solvent is not particularly limited as long as it dissolves 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, imbutyl 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),
Examples include ketones (methyl isobutyl ketone, cyclohexanone, etc.), halogenated hydrocarbons (1,2-ethylene dichloride, dichlorobenzene, etc.), and mixed solvents thereof. There are no restrictions on the above mixing method; all the components may be mixed in the solvent at once, or, if necessary, one or more of the components may be dissolved separately in the same or different solvents. Each surface protection material of the present invention can also be prepared by preparing two or more solutions and then mixing these solutions.

The concentration when mixing in a solvent is not particularly limited and is appropriately selected depending on the purpose of use and coating method, but usually 1
It is preferable for use to be about 0 to 80% by weight.

Further, a solvent-free mixture can be used. For example, the constituent components of each surface protection material of the present invention can be sufficiently mixed in a heated molten state, a solid state, etc., and then used.

In the present invention, the color filter includes color filters commonly used for applications such as liquid crystal display elements and solid-state image sensors, and are usually used by dyeing methods, dye dispersion methods, pigment dispersion methods, printing methods, electrodeposition methods, etc. It is manufactured by the method of

Examples of methods for applying each surface protective material of the present invention onto a color filter include applying each surface protective material of the present invention in a solution or heated molten state onto a color filter using spin cord coating, roll coating, bar coating, etc. The coating is usually applied to a coating thickness of 0.2 to IO μm by a method such as coater coating, spray coating, or printing coating.

In the method (Z-1) for forming a surface protective film 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. The unexposed areas are treated with an aqueous alkaline solution (aqueous solution of bases such as alkali metal carbonates such as sodium carbonate, hydroxides, alkali metal hydroxides such as IJium, and organic alkalis such as tetramethylammonium hydroxide). Since it is dissolved and removed by development, it is possible to form a surface protective layer consisting of a coating film only on the predetermined area. After this, if it is necessary to further complete the curing of the coating film, the above-mentioned active energy ray irradiation and/or heat treatment may be performed. 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 formation method (Z-1)
), a surface protective layer consisting of a coating film only on the predetermined area is first formed by applying, exposing, and developing operations. Next, at a temperature of usually 80 to 250°C, usually for 5 minutes to
A surface protective layer can be formed by heat-treating for about 120 minutes in the same manner as the method exemplified above and further curing the cured film by thermal polymerization and crosslinking.

The cured film formed in this way can be used as a surface protective film when manufacturing color filters by dye dispersion method, pigment dispersion method, printing method, electrodeposition method, etc., or as a surface protective film when manufacturing color filters by dyeing method. In such cases, it can be used as a surface protective film and/or a dye resisting film for a dyed layer.

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

Example 1 Acrylic acid/benzyl acrylate) (19/5lfi
r amount ratio) copolymer (weight average molecular weight 23,000.
After homogeneously dissolving 34 parts of carboxyl group content (35 mol%), 3 parts of 2-hydroxyethyl acrylate, 8 parts of trimethylolpropane triacrylate, 2 parts of 1-hydroxycyclohexylphenyl ketone, and 72 s of ethyl cellosolve acetate, the particle size was 0.2 μm. The surface protection material of the present invention was obtained by filtration using a filter. The surface protective material was spin-footed onto a glass substrate having a color filter pattern with a thickness of 1.7 μm, and then beta-treated at 80° C. for 10 minutes to obtain a coating film with a thickness of 2.0 μm. Then, it was heated for 500mj using an ultra-high pressure mercury lamp through a negative mask.
After exposure to light of /cm2, spray development using a 1% sodium carbonate aqueous solution at 30°C for 1 minute, spray rinsing with water for 1 minute, and apply a surface protective layer only to the exposed area on the color filter. was formed. Table 1 shows the evaluation results of the pencil hardness, tape peel adhesion, and chemical resistance of the obtained surface protective layer.

Example 2 35 parts of acrylic acid/n-butyl methacrylate (18/82 weight ratio) copolymer (weight average molecular weight 20,000, carboxyl group content 30 mol%), 4 parts of 2-hydroxyethyl acrylate, 2 parts of trimethylolpropane triacrylate, triglycidyl isocyanurate/acrylic acid (1/3 molar ratio) Reactant 79. 2-Methyl-[4'-(methylthio)phenyl]-2-morpholino 1-prono<non 2 1 part and 75 parts of ethyl cellosolve acetate were uniformly dissolved and filtered through a 0.2 μm filter to obtain a surface protection material of the present invention.

Using the above surface protection material, apply, expose, and
Development and rinsing were performed to form a surface protective material layer only on the exposed areas on the color filter. This was heat-treated at 150° C. for 30 minutes to form a surface protective layer.

Table 13 shows the evaluation results of the pencil hardness, tape peel adhesion and chemical resistance of the obtained surface protective layer.

Example 3 33 parts of methacrylic acid/ethyl acrylate/α-methylstyrene (23/17/lie weight ratio) copolymer (weight average molecular weight 20,000, carboxyl group content 28 mol%), pentoerythritol triac 1 ru) 1
0 parts, 2,2-dimethoxy-2-, 2 parts of phenylacetophenone and 70 parts of ethyl cellosolve acetate were uniformly dissolved and filtered through a 0.2 μm filter to obtain the surface protection material of the present invention. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 4 37 parts of the copolymer used in Example 1, 5 parts of 2-hydroxyethyl acrylate, 6 parts of trimethylolpropane triacrylate, 2-(4-methoxyphenyl)-4
, [i-bis(trichloromethyl)-s-)riazine 2
0.2 parts, 25 parts of hexahydrophthalic acid diglycidyl ester, 2 parts of l-benzyl-2-methylimidazole and 115 parts of ethyl cellosolve acetate were uniformly dissolved.
The surface protection material of the present invention was obtained by filtration with a μm filter. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 5 Acrylic acid/methyl methacrylate/benzyl acrylate
) C22722756 weight ratio) copolymer (weight average molecular weight 30.000, carboxyl group content 35 mol%
) 34 parts, bent erythritol triacrylate 8m
, 2 parts of 1-hydroxycyclohexylphenyl ketone,
5 parts of trimellidic anhydride, 2 parts of γ-glycidoxypropyltrimethoxysilane, 6 parts of ethyl cellosolve acetate
5 parts and 15 parts of diethylene glycol dimethyl ether
The surface protection material of the present invention was obtained by uniformly dissolving 30 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate in 40 parts of ethyl cellosolve acetate. Obtained.

This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 6 38 parts of the copolymer used in Example 3, 6 parts of 2-hydroxyethyl acrylate, 7 parts of triglycidyl isocyanurate/acrylic acid (molar ratio of l/3) reactant, 2-methyl-[4' 2 parts of -(methylthio)phenyl]-2-morpholino-1-propanone, 1. After homogeneously dissolving 24 parts of G-hexanediol diglycidyl ether, 5 parts of bis(3,4-epoxycyclohexylmethyl)adipate, 2 parts of γ-glycidoxyprobyltrimethoxysilane and 125 parts of ethyl cellosolve acetate, a 0.2 μm solution was obtained. The surface protection material of the present invention was obtained by filtration with a filter. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 7 Acrylic acid/benzyl acrylate (45/55 weight ratio) copolymer (weight average molecular weight approximately 15,000, carboxyl base content 65 mol%) 50 parts, glycidyl methacrylate 27.4 parts, hydroquinone monomethyl ether 0 .2 g, 0.3 parts of benzyltriethylammonium chloride were dissolved in 115 parts of ethyl cellosolve acetate, and reacted at 100 °C for 10 hours to obtain a reactant solution with a nonvolatile content of 41% by weight, an acid value of 3B, and 5 mg K OH/g ( A-2a) was obtained. This reactant solution (A-2a) 85
parts, 10 parts of pentaerythritol triacrylate, 2 parts
, 2 parts of 2-dimethoxy-2-phenylacetophenone and 20 parts of ethyl cellosolve acetate were uniformly dissolved.
．． The surface protection material of the present invention was obtained by filtration with a 2 μm filter. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 8 Methacrylic acid/ethyl acrylate/α-methylstyrene (52/G/42 weight ratio) copolymer (weight average molecular weight approximately 15.000, carboxyl group content 59 mol%)
50 parts of glycidyl acrylate, 22.9 parts of hydroquinone monomethyl ether, 0.2 parts of hydroquinone monomethyl ether, and 0.3 parts of benzyltriethylammonium chloride were dissolved in 110 parts of ethyl cellosolve acetate, and reacted at 100°C for 10 hours to obtain a non-volatile content of 42% by weight. Acid value 3B, Om g K OH/
A reactant solution (A-2b) of g was obtained. This reactant solution (
A-2b) 90 parts, 2-hydroxyethyl acrylate 5 parts, trimethylolpropane triacrylate 8 parts, 2-methyl-[4'-(methylthio)phenyl]-
2 parts of 2-morpholino-1-propanone, 2 parts of γ-glycidoxypropyl trimethoxysilane and 25 parts of ethyl cellosolve acetate were uniformly dissolved and filtered through a 0.2 μm filter to obtain the surface protection material of the present invention. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 9 87 parts of the reactant solution (A-2a) used in Example 7, 2
-4 parts of hydroxyethyl acrylate, 6 parts of pentaerythritol triacrylate, 2 parts of 2-(4-methoxyphenyl)-4,B-bis(trichloromethyl)-8-triazine, 2,2-bis(4-hydroxycyclohexyl) 15 parts of propane diglycidyl ether, 1, 6-
15 parts of hexanediol diglycidyl ether, 2 parts of 1-benzyl-2-methylimidazole, 2 parts of γ-glycidoxypropyl trimethoxysilane and 70 parts of ethyl cellosolve acetate were uniformly dissolved and filtered through a 0.2 μm filter. A surface protection material of the present invention was obtained. This was evaluated in the same manner as in Example 2, and the results are shown in Table 1.

Example 10 88 parts of the reactant solution (A-2b) used in Example 8, 12 parts of pentaerythritol triacrylate, 2 parts of 1-hydroxycyclohexylphenyl ketone, 3,4-epoxycyclohexylmethyl-3,4- 30 parts of epoxycyclohexane carboxylate, 5 parts of trimellidic anhydride
1 part, 2 parts of γ-glycidoxypropyltrimethoxysilane and 75 parts of ethyl cellosolve acetate were uniformly dissolved and filtered through a 0.2 μm filter to obtain the surface protection material of the present invention. Table 1 shows the results of evaluating this in the same manner as in Example 2.
Shown below.

Table-1 (Note) Evaluation method; Pencil hardness; JIS K-5400 tape peeling;
J I S D-0202 Liquid resistance; C-35% hydrochloric acid aqueous solution, 40℃ x min (1-10% Na011 aqueous solution, 40℃ x 15 min e-N-methylpyrrolidone, room temperature x
Appearance change after 2 hours immersion ○: No change [Effect of the invention

Claims (1)

[Claims] 1. Copolymer of (meth)acrylic acid and vinyl monomer (
A-1), photopolymerizable monomer (B) and photoinitiator (
A surface protection material for a color filter, characterized by being formed by combining C). 2. Copolymer of (meth)acrylic acid and vinyl monomer (
A-1), photopolymerizable monomer (B), photoinitiator (C)
A surface protective material for a color filter, comprising a combination of an epoxy compound (D) having at least two epoxy groups in the molecule and an epoxy curing agent (E). 3. Copolymer of (meth)acrylic acid and vinyl monomer (
The surface of a color filter characterized by a combination of a reaction product (A-2) of A-1) and glycidyl (meth)acrylate, a photopolymerizable monomer (B), and a photopolymerization initiator (C). Protective layer. 4. 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) and an epoxy curing agent (E) in combination, a surface protection material for a color filter. 5. After applying the surface protection material according to claim 1 or 3 onto a color filter, only predetermined areas are irradiated with active energy rays, and uncured parts are removed by development treatment with an alkaline aqueous solution, and if necessary, active energy rays are applied. A method for forming a surface protective layer of a color filter, which comprises irradiation with radiation and/or heat treatment. 6. After applying the surface protection material according to claim 2 or 4 on a color filter, irradiating only a predetermined portion with active energy rays, uncured portions are removed by development treatment with an alkaline aqueous solution, and then heat treatment is performed. A method for forming a surface protective layer of a color filter, characterized by: