JPH04315102A - Coating resin composition and resin composition for color filter protective film - Google Patents

Abstract

PURPOSE:To provide the coating resin composition capable of forming a smooth coating film extremely excellent in transparency, adhesiveness, resistances to water, chemicals, heat, scratching, and the like and useful for forming coating films for many kinds of articles, especially, the color filter protective film. CONSTITUTION:The coating resin composition characterized by comprising [A] a copolymer obtained by copolymerizing (a) N-substituted maleimide, (b) 4-8C tertiary alkyl methacrylate, (c) acrylic acid/or methacrylic acid, and (d) when needed, an unsaturated monomer copolymerizable with the components (a)-(c), and [B] an epoxy resin having >=2 epoxy groups in the molecule.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coating and a resin composition for color filter protective films.

0002

2. Description of the Related Art Coating films are often formed for the purpose of preventing deterioration and damage to the surfaces of various articles. Such a coating film must have a smooth coating film, high adhesion to the substrate, toughness, excellent water resistance, chemical resistance and solvent resistance, heat resistance and Performance such as high light resistance and no deterioration over a long period of time is required.

[0003] In recent years, liquid crystal display elements, solar cells,
In addition to the above-mentioned performance, coating films used for optical disks and the like are increasingly being used for applications that require transparency. For example, in recent years, various color liquid crystal display elements with built-in color filters have been announced. In producing this color liquid crystal display element, a color filter is provided on a transparent substrate such as glass, and indium tin oxide (
A method is becoming mainstream in which a transparent electrode is formed by depositing an inorganic thin film made of ITO or the like and patterned by photolithography, and then a liquid crystal is further placed on top of the transparent electrode. In this case, the color filter has an IT
Since it does not have enough heat resistance and chemical resistance to withstand the process of vapor-depositing O and forming transparent electrodes using photolithography, a protective film is formed on the color filter before vapor-depositing ITO. There is a need.

Properties required of this color filter protective film include, in addition to heat resistance and chemical resistance, adhesion to glass substrates and color filters, coating properties, transparency, and scratch resistance. Among these, heat resistance is required to be stable under these conditions because the surface of the protective film is usually heated to 200° C. or higher when a transparent electrode such as ITO is formed on the protective film by vapor deposition.

[0005] As a coating material with excellent heat resistance and chemical resistance, Japanese Patent Application Laid-Open No. 1965-1980
Acrylic resins described in JP-A No. 6 and JP-A-62-119501, polyglycidyl methacrylate-based resins described in JP-A-60-216307, JP-A-63-13
Melamine resins, epoxy resins, and other polyimide resins described in Japanese Patent No. 1103 have been proposed.

However, each of the conventionally proposed materials has drawbacks, and a well-balanced material that satisfies all required properties has not yet been developed. For example, acrylic resins have insufficient heat resistance, and there is a problem in that wrinkles and cracks occur on the surface of the film during vapor deposition of ITO and the like. In addition, polyglycidyl methacrylate resins have insufficient adhesion to glass substrates, etc., causing peeling during the liquid crystal element assembly process, and cannot sufficiently prevent chemicals from entering the color filter layer. Can not. Furthermore, although melamine resin has relatively high heat resistance, it has extremely poor adhesion to glass substrates and color filters, and is likely to cause repellency on the substrates and filters. On the other hand,
Epoxy resins with good adhesion have insufficient heat resistance, and those with high heat resistance have poor adhesion and coating properties, making it impossible to balance required properties. Further, polyimide resins have problems such as insufficient transparency, poor storage stability of varnishes, and the fact that only solvents that attack color filters can be used.

[0007]

OBJECTS OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art, and to improve heat resistance, chemical resistance, adhesion,
The object of the present invention is to provide a novel coating resin composition and a color filter protective film resin composition that are well-balanced and can satisfy all required properties such as coating properties, transparency, and scratch resistance.

[0008]

[Means for Solving the Problems] The present invention is based on A. (a)N
Substituted maleimide, (b) methacrylic acid ester of a tertiary alcohol having 4 to 8 carbon atoms, (c) acrylic acid and/or methacrylic acid, and (d) optionally (a) to (c)
A copolymer resin obtained by copolymerizing an unsaturated monomer copolymerizable with the component; and B. The present invention relates to a coating resin composition containing an epoxy resin having two or more epoxy groups in the molecule, and a color filter protective film resin composition using the same.

In the resin composition of the present invention, (a) N as a monomer component constituting the copolymer resin as component A
Substituted maleimides include N-methylmaleimide, N-
Examples include N-alkylmaleimides such as ethylmaleimide, N-propylmaleimide, and N-butylmaleimide, N-cycloalkylmaleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, and N-alkylphenylmaleimide, and one type of these The above are used. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferred from the viewpoint of heat resistance and adhesion to the substrate. The amount of N-substituted maleimide (a) in the copolymer resin as component A is preferably 20 to 70% by weight. When the amount is less than this, the resulting coating film tends to have insufficient heat resistance, and when it is more than this, there is a tendency for problems in adhesion and coating properties to occur.

The methacrylic acid ester of a tertiary alcohol having 4 to 8 carbon atoms as component (b) includes t-butyl methacrylate, t-amyl methacrylate, t-hexyl methacrylate, t-heptyl methacrylate, t-octyl methacrylate, etc. Among them, t-butyl methacrylate and t-amyl methacrylate are preferred from the viewpoint of heat resistance. The methacrylic acid ester of a tertiary alcohol having 4 to 8 carbon atoms is preferably contained in the copolymer resin in an amount of 10
~60% by weight is blended. When the amount is less than this, coating properties and adhesion tend to deteriorate, and when it is more than this, the heat resistance tends to be insufficient.

The amount of acrylic acid and/or methacrylic acid as component (c) is preferably 5 to 30% by weight in the copolymer resin. If the amount is less than this, the heat resistance and scratch resistance of the resulting cured product will tend to be insufficient, and if it is more than this, the coating properties, chemical resistance, etc. of the cured product will tend to decrease.

[0012] Component A in the present invention includes the above (a) to
In addition to (c) component, if necessary, (d) component (a) ~
It may contain an unsaturated monomer copolymerizable with component (c) as a constituent monomer. Examples of such unsaturated monomers include unsaturated fatty acid esters, aromatic vinyl compounds, and vinyl cyanide compounds.

Examples of unsaturated fatty acid esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, cyclohexyl acrylate, and tricyclo acrylate [5.2.1.02' 6] Dec-8-yl ester,
Acrylic acid cycloalkyl esters such as isobornyl acrylate and norbornyl acrylate; acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate; acrylic acid esters such as glycidyl acrylate and 2-hydroxyethyl acrylate; methyl methacrylate; Alkyl methacrylates, cyclohexyl methacrylate, tricyclo methacrylate [5.2. 1.02'6] Dec-8-yl ester, isobornyl methacrylate, methacrylic acid cycloalkyl ester such as norbornyl methacrylate, methacrylic acid aromatic ester such as phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, methacrylic acid 2 -methacrylic acid esters such as hydroxyethyl.

[0014] Examples of aromatic vinyl compounds include styrene,
Examples include α-substituted styrenes such as α-methylstyrene and α-ethylstyrene, and nuclear-substituted styrenes such as chlorostyrene, vinyltoluene, and t-butylstyrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile. these(
The unsaturated monomer copolymerizable with components (a) to (c) of component d) is used in an amount of 0 to 50% by weight in the copolymer resin of component A. If it exceeds 50% by weight, the effects of the present invention cannot be sufficiently obtained.

In copolymerizing these components (a) to (d), known methods such as radical polymerization and ionic polymerization can be applied. For example, it can be produced by methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization in the presence of a polymerization initiator.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate, and t-butylperoxy-2-
Organic peroxides such as ethylhexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4
- Azo compounds such as methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azodibenzoyl, water-soluble catalysts such as potassium persulfate, ammonium persulfate, and peroxides or persulfates. Any catalyst that can be used in normal radical polymerization can be used, such as a redox catalyst using a combination of reducing agents. The polymerization catalyst is preferably used in an amount of 0.01 to 10% by weight based on the total amount of components (a) to (d).

Further, as a polymerization regulator, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer, etc. may be added as necessary for controlling the molecular weight. The polymerization temperature can be appropriately selected within the range of 0 to 200°C, preferably 50 to 120°C. A
The weight average molecular weight of the component copolymer resin is 10,000~
Preferably it is 100,000. If it is too low, the strength and adhesion of the coating film tend to be poor, and if it is too high, the leveling properties of the coating film tend to be poor.

[0019] As the solvent for solution polymerization, the solvents used in ordinary radical polymerization can be used. Specific examples include aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran,
Ether solvents such as dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethyl acetate, acetic acid-n-
Propyl, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Ester solvents such as acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; dimethylformamide,
Examples include amide solvents such as dimethylacetamide and N-methylpyrrolidone. Among these solvents, ester solvents and ketone solvents are preferred, used alone or in combination
More than one type can be used in combination. When used as a resin composition for coating, it usually contains a solvent, so it is preferable to polymerize by solution polymerization using the same solvent. It is also possible to use it by separating it and dissolving it in another solvent.

The resin composition of the present invention contains, as component B, an epoxy resin having two or more epoxy groups in the molecule. Such epoxy resins include bisphenol A
type liquid epoxy resin, bisphenol A type solid epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin Although there are resins, phenol novolac epoxy resins and cresol novolac epoxy resins are particularly preferred from the viewpoint of heat resistance and adhesiveness.

The mixing ratio of component A and component B in the composition of the present invention is preferably such that 30 to 300 parts by weight of the epoxy resin as component B is blended to 100 parts by weight of the copolymer resin as component A. If the amount of the epoxy resin as component B is too small, chemical resistance tends to be insufficient, and if it is too large, adhesion tends to decrease.

The coating resin composition of the present invention includes:
Various components other than the above-mentioned A and B components can be used as necessary. First, it is preferable to use at least one compound selected from polycarboxylic anhydrides and polycarboxylic acids from the viewpoint of improving heat resistance and scratch resistance.

[0023] Examples of the polyhydric carboxylic acid anhydride include:
Itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride , aliphatic dicarboxylic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride; aliphatic polycarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, 3,3', 4,4'-
Examples include aromatic polycarboxylic acid anhydrides such as diphenylsulfone tetracarboxylic dianhydride; ester group-containing anhydrides such as ethylene glycol bistrimelitate and glycerin tristrimelitate. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as itaconic acid, maleic acid, succinic acid, citraconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, and cyclopentanetetracarboxylic acid; Aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid can be mentioned. These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids may be used alone or in combination of two or more types, but aromatic polyvalent carboxylic acid anhydrides and aromatic polyvalent carboxylic acids are heat-resistant. Trimellitic anhydride is preferred from the viewpoint of the balance between heat resistance and solubility in solvents.

When using at least one compound selected from polycarboxylic anhydrides and polycarboxylic acids, the amount is 5 to 5 parts by weight per 100 parts by weight of the copolymer resin as component A.
It is preferable to use it in a range of 0 parts by weight. If the amount is less than this, the effect of use will not be sufficiently obtained, and if it is more than this, coating properties, chemical resistance, etc. will be deteriorated.

[0025] Furthermore, a coupling agent may be added to the composition of the present invention in order to improve adhesion. The coupling agent is preferably a functional silane coupling agent, and specifically a silane coupling agent having a reactive substituent such as a vinyl group, methacryloyl group, hydroxyl group, carboxyl group, amino group, isocyanate group, or epoxy group. is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ
Examples include -glycidoxypropyltrimethoxysilane, and silane coupling agents having epoxy groups are particularly preferred because they have excellent adhesive properties and solvent resistance. These functional silane coupling agents may be used alone or in combination of two or more. The amount of the functional silane coupling agent used is 0 when the total amount of the copolymer resin of component A and the epoxy resin of component B is 100 parts by weight.
．． The amount is preferably in the range of 1 to 10 parts by weight; if it is less than this, the effect of use will not be sufficient, and if it is more than this, chemical resistance etc. will be reduced.

[0026] The composition of the present invention can usually be dissolved in a solvent, applied, and cured by heating to form a coating film. The solvent is not particularly limited as long as it dissolves the composition of the present invention and does not react with these components. Specifically, the solvents exemplified as solvents for solution polymerizing the copolymer resin, which is component A of the present invention, may be mentioned. Among these solvents, ester solvents and ketone solvents are preferred, and they can be used alone or in combination of two or more.

[0027] The method of preparing a composition solution by dissolving the composition of the present invention in a solvent is not particularly limited.
A composition solution may be prepared by dissolving all the components in a solvent at the same time, or if necessary, each component may be prepared as two or more solutions and mixed at the time of use to form a composition solution. . When preparing a composition solution in this way, the amount of solvent used is preferably 50 to 95% by weight of the total amount of the final composition solution to be applied. If the amount of solvent used is less than 50% by weight, the solid content concentration may be too high and the leveling property of the coating film may decrease or the transparency of the coating film may decrease, whereas if it exceeds 95% by weight. If the solid content concentration is too low, the chemical resistance of the coating film may be insufficient. The composition of the present invention preferably has a viscosity of 5 to 100 centipoise (25°C), although it depends on the solid content concentration. If it is too low, the desired film thickness may not be achieved.
If it is too high, the leveling properties of the coating film tend to deteriorate.

[0028] The composition of the present invention may also contain, if necessary,
Curing accelerators, antioxidants, stabilizers such as ultraviolet absorbers, etc. used for curing general epoxy resins may be added to the extent that transparency is not impaired.

The method of applying the composition solution of the present invention is not particularly limited, and includes, for example, a dipping method, a spray method, a roll coating method, a spin coating method, and a printing method such as screen printing and offset printing. and so on.

The heat curing conditions for the composition of the present invention are appropriately selected depending on the specific type and blending ratio of each component of the composition, but are usually 50 to 300°C for 0.1 to 10 hours, preferably 100°C. It is about 1 to 5 hours at ~250°C.

[0031] The coating film formed from the composition of the present invention thus obtained exhibits excellent adhesion to various materials such as glass, metal, and plastic, and is smooth, strong, light resistant, and heat resistant. It is useful as a coating film for various articles because it has excellent properties such as hardness, water resistance, solvent resistance, and transparency. In particular, as color filter protective films, surface protective layers and anti-dye protective layers of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resins with dyes or by dispersing pigments are used. It is useful as When used as a color filter protective film, the film thickness after heat curing is 0.
．． It is used by appropriately coating it to a thickness of about 0.05 to 30 μm, preferably about 0.1 to 10 μm.

[0032]

[Examples] The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 100 parts by weight of cellosolve acetate (acetoxyethoxyethane) was charged into a 1-liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel, and the inside of the flask was purged with nitrogen. . 75 parts by weight of N-phenylmaleimide, 45 parts by weight of t-butyl methacrylate,
30 parts by weight of methacrylic acid and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate, and 80 parts by weight of methacrylic acid was dissolved in 350 parts by weight of cellosolve acetate in a nitrogen stream.
The mixture was added dropwise at ℃ over 3 hours. Furthermore, after stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained at this temperature for 2 hours. The obtained copolymer resin solution has a viscosity of 43 poise (25°C)
and nonvolatile content 25.2% by weight (180°C, 1 hour,
(according to JISC-2103), acid value 32.0 (mg K
OH/g).

400 parts by weight of this copolymer resin solution was added with cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.; EO
CN-102S, epoxy equivalent 214 (g/eq), softening point 75°C) 50 parts by weight, trimellitic anhydride 10 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.; SH -60
40) 1.6 parts by weight and 375 parts by weight of cellosolve acetate were added and mixed uniformly at room temperature to dissolve. The resulting solution had a viscosity of 47 centipoise (25°C) and a nonvolatile content of 20.0% by weight (180°C, 1 hour).

After filtering this solution through a membrane filter with a pore size of 0.2 μm, a glass plate (Dow Corning 7059 material, alkali-free glass) was coated using a spin coater.
The coating was applied by spinning at a rotation speed of 2000 rpm. After application,
The glass plate was heat-treated in a constant temperature bath at 180° C. for 1 hour to cure the coating film. The surface of the resulting coating film was extremely smooth and no pinholes were observed. The film thickness measured by a two-beam interference microscope was 1.2 μm.

The following tests were conducted on the coating film thus prepared. In order to examine the adhesion of the coating film to the glass plate, a cross-cut test (JIS-K-54) was performed using tape peeling.
00) was performed. As a result, the number of remaining samples was 100/100, and no peeling was observed. Next, 400n of coating film
When the absorption spectrum in m to 800 nm was measured using the same glass plate used for the above coating as a control, the light transmittance was 90% or more in the entire region. In addition, the glass plate with this coating was tested in a pressure cooker (120°C, 2 atm) for 10 hours, then immersed in N-methylpyrrolidone for 30 minutes at room temperature, and then immersed in a 5% by weight aqueous sodium hydroxide solution for 30 minutes at room temperature. After immersion, they were left in a gear oven at 250° C. for 1 hour and then subjected to the above-mentioned cross-over test and light transmittance measurement, but no decrease in adhesiveness or light transmittance was observed in either case. Note that Table 1 shows the results of the cross-over test, and Table 2 shows the measurement results of light transmittance. Furthermore, the surface hardness of the coating film was determined by pencil hardness (JIS-K-5
400), and the results are shown in Table 3.

Example 2 100 parts by weight of cellosolve acetate was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and the inside of the flask was purged with nitrogen. 75 parts by weight of N-phenylmaleimide, 37.5 parts by weight of t-butyl methacrylate, 37.5 parts by weight of methacrylic acid and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate. The mixture was added dropwise to a liter flask at 80°C in a nitrogen stream over 3 hours. Furthermore, after stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained at this temperature for 2 hours. The obtained copolymer resin solution had a viscosity of 68 poise (25°C), a nonvolatile content of 25.6% by weight (180°C, 1 hour), and an acid value of 41.0 (mg KOH).
/g).

Cresol novolak epoxy resin (Nippon Kayaku Co., Ltd.; EO
CN-103S, epoxy equivalent 218 (g/eq), softening point 85°C) 65 parts by weight, trimellitic anhydride 10 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.; SH -60
40) 1.8 parts by weight and 500 parts by weight of cellosolve acetate were added, mixed uniformly at room temperature, and dissolved. The resulting solution had a viscosity of 52 centipores (25°C) and a nonvolatile content (180°C, 1 hour) of 18.2% by weight. The obtained solution was applied onto a glass plate in the same manner as in Example 1, heated and cured, and various properties of the coating film were evaluated. The results are shown in Tables 1 to 3.

Example 3 100 parts by weight of cellosolve acetate was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and the inside of the flask was purged with nitrogen. 75 parts by weight of N-cyclohexylmaleimide, 45 parts by weight of t-butyl methacrylate, 30 parts by weight of methacrylic acid and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate and placed in the 1 liter flask described above. The mixture was added dropwise over 3 hours at 80°C in a nitrogen stream. Furthermore, after stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained at this temperature for 2 hours.

400 parts by weight of the obtained copolymer resin solution was added with cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.;
EOCN-102S) 50 parts by weight, trimellitic anhydride 10 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.; S
1.6 parts by weight of H-6040) and 375 parts by weight of cellosolve acetate were added and uniformly mixed and dissolved at room temperature. The resulting solution had a viscosity of 42 centipoise (25°C) and a nonvolatile content of 20.8% by weight (180°C, 1 hour). The obtained solution was applied onto a glass plate in the same manner as in Example 1, heated and cured, and various properties of the coating film were evaluated. The results are shown in Tables 1 to 3.

Example 4 100 parts by weight of cellosolve acetate was charged into a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel, and the inside of the flask was purged with nitrogen. 75 parts by weight of N-phenylmaleimide, 45 parts by weight of t-amyl methacrylate, 30 parts by weight of methacrylic acid and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate, and the mixture was placed in the 1 liter flask described above. The mixture was added dropwise over 3 hours at 80°C in a nitrogen stream. After further stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained at this temperature for 2 hours.

400 parts by weight of the obtained copolymer resin solution was added with cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.;
EOCN-102S) 50 parts by weight, trimellitic anhydride 10 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.; S
1.6 parts by weight of H-6040) and 375 parts by weight of cellosolve acetate were added and uniformly mixed and dissolved at room temperature. The resulting solution had a viscosity of 38 centipoise (25°C) and a nonvolatile content of 19.8% by weight (180°C, 1 hour). The obtained solution was applied onto a glass plate in the same manner as in Example 1, heated and cured, and various characteristics of the coating film were evaluated. The results are shown in Tables 1 to 3.

Comparative Example 1 10 parts by weight of cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.; EOCN-103S), 3 parts by weight of trimellitic anhydride, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.) Company;S
H-6040) 0.1 part by weight and 40 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, the resulting solution was applied on a glass plate in the same manner as in Example 1, and heated and cured.
Various properties of the coating film were investigated. The results are shown in Tables 1 and 2.

Comparative Example 2 6 g of polyglycidyl methacrylate (weight average molecular weight in terms of polystyrene of about 80,000), 0.0 g of trimellitic anhydride.
6g, γ-glycidoxypropyltrimethoxysilane (
Toray Dow Corning Silicone Co., Ltd.; SH-6
040) 0.3 g and 35 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, and the resulting solution was applied onto a glass plate in the same manner as in Example 1, heated and cured, and various property tests of the coating film were performed. went. The results are shown in Tables 1 and 2.

[0045] In Tables 1 and 2, the symbols have the following meanings. PCT = pressure cooker test (120°C, 2 atm) NMP = immersed in N-methylpyrrolidone NaOH = immersed in 5% by weight aqueous sodium hydroxide solution

0
046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

Example 5 Using the composition solutions prepared in Examples 1 to 4, suitability for color filter substrates was investigated. As a test method, a color filter base material was prepared using a generally known method, and the applicability and heat resistance on this base material were examined. To prepare the color filter base material, first, an aqueous solution of gelatin and ammonium dichromate (10:1 weight ratio) was spin-coated on a transparent glass substrate so that the film thickness after drying was 1 μm.
Dry at ℃ for 10 minutes, irradiate the resulting coating with ultraviolet light,
A dyed substrate layer was obtained by developing with pure water. This was dyed red by immersing it in a red dyeing bath consisting of 2 g of Suminol Milling Red RS (manufactured by Sumitomo Chemical Co., Ltd.), 3 g of acetic acid, and 100 g of distilled water, washing with water, and drying at 150°C for 30 minutes. A color filter base material was formed.

Next, the composition solutions prepared in Examples 1 to 4 were spin-coated onto the color filter base material at 2000 rpm, and dried at 180° C. for 1 hour to form a protective layer. Indium tin oxide (ITO) was deposited by a conventional method on the thus prepared color filter with a protective layer, and then patterned by photolithography.

[0051] The color filter having the ITO pattern obtained in this way was observed in detail using an optical microscope, and no defects such as wrinkles or cracks were observed on the color filter or the protective film, and the adhesiveness between the color filter and the protective film was not observed. The adhesion was also good.

[0052]

[Effect of the invention] The coating resin composition of the present invention has
Smooth, transparent, adhesive, water resistant, chemical resistant, heat resistant,
It forms a coating film with excellent scratch resistance, and is useful as a coating material for various articles, especially as a color filter protective film material.

Claims (5)

[Claims] [Claim 1] A. (a) N-substituted maleimide, (b)
Methacrylic acid ester of a tertiary alcohol having 4 to 8 carbon atoms, (c) acrylic acid and/or methacrylic acid, and (
d) A copolymer resin obtained by copolymerizing an unsaturated monomer copolymerizable with components (a) to (c) as required; and B. A coating resin composition comprising an epoxy resin having two or more epoxy groups in its molecule. 2. The coating resin composition according to claim 1, further comprising at least one compound selected from polycarboxylic anhydrides and polycarboxylic acids. 3. Claim 1 or 2, wherein the N-substituted maleimide is at least one selected from the group consisting of N-alkylmaleimide, N-cycloalkylmaleimide, N-phenylmaleimide, and N-alkylphenylmaleimide.
The coating resin composition described above. 4. Claim 1, wherein the epoxy resin is at least one selected from the group consisting of phenol novolac epoxy resin and cresol novolac epoxy resin.
3. The coating resin composition according to 2 or 3. 5. A resin composition for a color filter protective film, comprising the coating composition according to claim 1 or 2.