JPH04272978A - Coating resin composition and resin composition for color filter protective film containing same - Google Patents

Abstract

PURPOSE:To provide a coating resin composition excellent in heat resistance, chemical resistance, transparency, adhesion, etc., and suited for especially a color filter protective film. CONSTITUTION:A coating resin composition comprising a copolymer resin prepared by copolymerizing an N-substituted maleimide (i) with an alicyclic acrylic ester having a 6-20 C alicyclic structure and/or an alicyclic methacrylic ester (ii) having a 6-20 C alicyclic structure, acrylic acid and/or methacrylic acid (iii), and optionally an unsaturated monomer coplymerizable with monomers (i)-(iii) and an epoxy resin having at least two 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 coating resin composition and a color filter protective film resin composition using the same.

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. In such a coating film, it is necessary to obtain a smooth coating film, have high adhesion to the substrate, be tough, have excellent water resistance, chemical resistance, 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 in optical discs and the like are increasingly being used for applications that require transparency and the like.

For example, in recent years, various color liquid crystal display elements incorporating 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, an inorganic thin film made of indium tin oxide (ITO), etc. is deposited on this, and transparent electrodes are formed by patterning using photolithography. A method in which liquid crystal is further placed on top of the liquid crystal after forming the liquid crystal is becoming mainstream. In this case, since the color filter does not have enough heat resistance and chemical resistance to withstand the process of vapor depositing ITO on it and forming transparent electrodes using photolithography, it is necessary to It is necessary to form a protective film on the color filter.

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

[0006] As such coating materials having excellent heat resistance, chemical resistance, etc., there are acrylic resins described in JP-A-58-196506 and JP-A-62-119501, and JP-A-60-216307. Polyglycidyl methacrylate resin described in JP-A-63-13110
Melamine resins, epoxy resins, and other polyimide resins described in Publication No. 3 have been proposed.

[0007]

[Problems to be Solved by the Invention] However, each of the conventionally proposed materials has drawbacks, and there is no well-balanced material that satisfies all required properties.

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.

[0009] Polyglycidyl methacrylate resin has insufficient adhesion to glass substrates, etc., and it is necessary to sufficiently prevent peeling during the liquid crystal element assembly process and infiltration of chemicals into the color filter layer. I can't.

Although melamine resin has relatively high heat resistance, it has extremely poor adhesion to glass substrates and color filters, and tends to cause repellency on the substrates and filters.

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 the required properties. Further, polyimide resins have problems such as insufficient transparency, poor storage stability of varnishes, and the fact that only solvents that can soak color filters can be used.

The purpose of the present invention is to solve the above-mentioned drawbacks of conventional materials and to create a new well-balanced material that can satisfy all required properties such as heat resistance, chemical resistance, adhesion, coating properties, transparency, and scratch resistance. The present invention provides a coating resin composition and a color filter protective film resin composition using the same.

[0013]

[Means for Solving the Problems] That is, the present invention provides
．． (1) N-substituted maleimide, (2) alicyclic acrylic ester and/or alicyclic methacrylic ester having an alicyclic structure having 6 to 20 carbon atoms, (3) acrylic acid and/or methacrylic acid, and ( 4) As necessary (
A copolymer resin obtained by copolymerizing an unsaturated monomer copolymerizable with 1) and/or (3); 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.

As (1) N-substituted maleimide as a monomer component constituting the copolymer resin which is component A in the present invention, known ones can be used, including N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-substituted maleimide, and N-substituted maleimide.
It is preferable to use at least one compound selected from the group consisting of butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-alkyl group-substituted phenylmaleimide from the viewpoint of heat resistance and adhesion to the substrate. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferred. In the copolymer resin that is component A

(1) The amount of N-substituted maleimide is 20~
It is preferably 70% by weight (based on the total amount of (1), (2), (3) and (4)). If the amount is less than this, the resulting coating film tends to have insufficient heat resistance, and if it is more than this, there is a tendency for problems with adhesion and coating properties to occur.

Examples of (2) alicyclic acrylic esters and alicyclic methacrylic esters having an alicyclic structure having 6 to 20 carbon atoms include cyclohexyl acrylate, cyclohexylmethyl acrylate, and 2,2 acrylic acid. ,5
-Trimethylcyclohexyl, norbornyl acrylate, norbornylmethyl acrylate, adamantyl acrylate, tricyclo acrylate [5,2,1,02'6]
Decan-8-yl, tricycloacrylate [5,2,1
,02'6]cycloalkyl acrylates such as decan-3 (or 4)-ylmethyl, bornyl acrylate, isobornyl acrylate, fentyl acrylate, menthyl acrylate, cyclohexyl methacrylate, cyclohexylmethyl methacrylate, methacrylic acid 2, 2,5-trimethylcyclohexyl, norbornyl methacrylate, norbornylmethyl methacrylate, adamantyl methacrylate, tricyclo methacrylate [5,2,1,02'6
]Decan-8-yl, tricyclo[5,2 methacrylate]
, 1,02'6]decane-3(or 4)-ylmethyl,
Examples include methacrylic acid cycloalkyl esters such as bornyl methacrylate, isobornyl methacrylate, fentyl methacrylate, and menthyl methacrylate, and one or more of these may be used. Among them, norbornyl methacrylate adamantyl methacrylate,
Preferred are methacrylic acid cycloalkyl esters containing condensed rings such as tricyclo[5,2,1,02'6]decane-8-yl methacrylate and isobornyl methacrylate.

(1) in the copolymer resin as component A
The amount of alicyclic acrylic ester and/or methacrylic ester used is 20 to 70% by weight ((1), (2)
, (3) and (4)). When the amount is less than this, the heat resistance of the resulting cured coating film tends to be insufficient, and when it is more than this, problems tend to occur in adhesion and coating properties.

The blending amount of acrylic acid and/or methacrylic acid (3) is 5 to 30% by weight (((
1), (2), (3) and (4)) is preferred. When the amount is less than this, the heat resistance and scratch resistance of the resulting cured product tend to be insufficient, and when it is more than this, the coating properties and the chemical resistance of the cured product tend to be reduced.

(4) (1), (2) and/or (
Examples of unsaturated monomers copolymerizable with 3) include unsaturated fatty acid esters other than (2), aromatic vinyl compounds, vinyl cyanide compounds, and the like. Examples of unsaturated fatty acid esters other than (2) include methyl acrylate, ethyl acrylate,
Acrylic acid alkyl esters such as butyl acrylate and 2-ethylhexyl 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; Methacrylic acid alkyl esters such as ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; methacrylic acid aromatic esters such as phenyl methacrylate and benzyl methacrylate; methacrylic acid esters such as glycidyl methacrylate and 2-hydroxyethyl methacrylate; and so on. Examples of the aromatic vinyl compound include styrene, 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.

[0020] These (4) (1), (2) and/
Alternatively, the unsaturated monomer copolymerizable with (3) is used in an amount of 0 to 50% by weight (based on the total amount of (1), (2), (3), and (4)) in the copolymer resin of component A. . When the amount is 50% by weight or more, the effect of the present invention tends to be insufficient.

These (1), (2), (3) and (
In copolymerizing 4), 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, t-butylperoxy-2-ethylhexanoate, and 1,1-di-t-butylperoxy. -Organic peroxides such as 3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-
Reduction with azo compounds such as methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl, water-soluble catalysts such as potassium persulfate, and ammonium persulfate, and peroxides or persulfates. Any compound that can be used in normal radical polymerization, such as a redox catalyst using a combination of agents, can be used. The polymerization catalyst is preferably used in an amount of 0.01 to 10% by weight based on the total amount of (1), (2), (3) and (4).

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 is preferably selected appropriately within the range of 0 to 200°C, particularly preferably 50 to 120°C.

[0025] As the solvent for solution polymerization, 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; Ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, and 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 Examples include ester solvents such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and γ-butyrolactone; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Among these solvents, ester solvents and ketone solvents are preferred and can be used alone or in combination of two or more. Generally, when used as a resin composition for coating, it contains a solvent, so it is preferable to polymerize by solution polymerization using the same solvent. It is also possible to isolate it and dissolve it in another solvent for use.

The epoxy resin having two or more epoxy groups in the molecule, which is component B in the present invention, includes bisphenol A type liquid epoxy resin, bisphenol A type solid epoxy resin, bisphenol F type epoxy resin, phenol novolak epoxy resin, Cresol novolac epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin,
Although there are heterocyclic epoxy resins, phenol novolac epoxy resins and cresol novolac epoxy resins are particularly preferred from the viewpoint of heat resistance and adhesion.

Regarding the mixing ratio of component A and component B in the composition of the present invention, it is preferable that 30 to 300 parts by weight of the epoxy resin as component B be 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:
If necessary, various components (C component) can be used in addition to the A and B components. As component C, it is preferable to use at least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids from the viewpoint of improving heat resistance and scratch resistance.

Examples of the polycarboxylic anhydride include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and anhydride. Aliphatic dicarboxylic anhydrides such as methylhexahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride; cyclopentanetetracarboxylic dianhydride,
Aliphatic polycarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, 3,3 Aromatic polyhydric carboxylic acid anhydrides such as ',4,4'-diphenylsulfonetetracarboxylic dianhydride; ester group-containing acid anhydrides such as ethylene glycol bistrimelitate and glycerin tristrimelitate; can. 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; phthalic acid , aromatic polyhydric carboxylic acids such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid.

[0030] These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids may be used as one type, or two or more types may be used in combination, but aromatic polyvalent carboxylic acid anhydrides and aromatic polyvalent carboxylic acids are heat resistant. Trimellitic anhydride is preferred in terms of properties, and trimellitic anhydride is particularly preferred in terms of the balance between heat resistance and solubility in solvents.

When using component C such as at least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids, copolymer resin 10 as component A is used.
It is preferable to use it in a range of 5 to 50 parts by weight based on 0 parts by weight. When the amount is less than this, it is difficult to obtain a sufficient effect of use, and when it is more than this, coating properties, chemical resistance, etc. are deteriorated.

[0032] Furthermore, a coupling agent may be added to the composition of the present invention in order to improve adhesion. As the coupling agent, a functional silane coupling agent is preferable, and 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, specifically, Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-Isocyanatopropyltriethoxysilane, γ-
Examples include glycidoxypropyltrimethoxysilane, and silane coupling agents having an epoxy group are particularly preferred because they have excellent adhesive properties, solvent resistance, and the like. Even if only one type of these functional silane coupling agents is used,
Two or more types may be combined. The amount of the functional silane coupling agent to be used is 0.5 parts by weight 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 tends to be insufficient, and if it is more than this, chemical resistance etc. tend to decrease.

[0033] 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.

The method of preparing a composition solution by dissolving the composition of the present invention in a solvent is not particularly limited, and the composition solution may be prepared by dissolving all the components in a solvent at the same time. 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 the composition solution in this manner, the amount of solvent used is preferably 50 to 95% by weight of the total amount of the final composition solution to be applied. 50
If it is less than 95% by weight, the solid content concentration is too high and the leveling properties of the coating film may be reduced or the transparency of the coating film may be reduced.On the other hand, if it exceeds 95% by weight, the solid content concentration is too low. The chemical resistance of the coating film may become insufficient. Furthermore, as necessary, stabilizers such as curing accelerators, antioxidants, and ultraviolet absorbers used in the curing of general epoxy resins may be added to the composition of the present invention to the extent that transparency is not impaired. It's okay.

The method of applying the composition solution of the present invention is not particularly limited, and includes coating methods such as dipping, spraying, roll coating, and spin coating, as well as printing methods such as screen printing and offset printing. . 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 and 0.1 to
It is about 10 hours, preferably about 1 to 5 hours at 100 to 250°C.

The coating film formed from the composition of the present invention thus obtained exhibits excellent adhesion to various materials such as glass, metals, and plastics, and is smooth, tough, light resistant, and heat resistant. Because of its excellent water resistance, solvent resistance, and transparency, it is useful as a coating film for various articles. In particular, gelatin is used as a color filter protective film.
It is useful as a surface protective layer and an anti-dye protective layer of various color filters obtained by dyeing various binder resins such as glue, polyvinyl alcohol, and acrylic resins with dyes or by dispersing pigments. When used as a color filter protective film, the film thickness after heat curing is 0.05~
It can be appropriately applied and used so as to have a thickness of about 30 μm, preferably about 0.1 to 10 μm.

[0037] In the prior art, coating properties, adhesion properties,
Although there was nothing that satisfied all the required properties such as heat resistance, by combining compounds with specific structures of the present invention,
It has become possible to satisfy each of these required characteristics in a well-balanced manner.

[0038]

[Examples] The present invention will be explained in detail with reference to Examples below, 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, 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 isobornyl methacrylate, 30 parts by weight of methacrylic acid, 0.0 parts by weight of azobisisobutyronitrile.
6 parts by weight were dissolved in 350 parts by weight of cellosolve acetate, and the solution was added dropwise to the aforementioned 1 liter flask at 80°C over 3 hours in a nitrogen stream. After further stirring at 80°C for 5 hours,
The temperature was raised to ℃ and kept for 2 hours. The obtained copolymer resin solution has a viscosity of 33 poise (25°C) and a nonvolatile content of 25.
2% by weight (180° C. for 1 hour, according to JIS C-2103), and an acid value of 32.5 (mgKOH/g).

Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.; EOC) was added to 400 parts by weight of this copolymer resin solution.
N-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-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 40 centipoise (25°C) and a nonvolatile content of 20
．． It was 2% by weight (180°C/1h).

[0040] This solution was filtered through a membrane filter with a pore size of 0.2 μm, and then spin coated on a glass plate (Dow Corning 7059 material, alkali-free glass) at a rotation speed of 2000 rpm using a spin coater. After coating, the glass plate was heated in a constant temperature bath at 180°C for 1 hour.
The coating was cured. The surface of the resulting coating film was extremely smooth and no pinholes were observed. The film thickness measured by a dual-light 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, the 400nm of the coating film
When the absorption spectrum at ~800 nm was measured using the same glass plate as the one on which the coating was applied as a reference, the light transmittance was 90% or more in the entire region.

[0042] Furthermore, after 10 hours of pressure cooker test (120°C, 2 atm) of the glass plate with this coating applied,
After 30 minutes of immersion in N-methylpyrrolidone at room temperature, 30 minutes of immersion in 5% sodium hydroxide aqueous solution at room temperature, and 250°C
After being left in a gear oven for 1 hour, the above-mentioned cross-cut test and light transmittance measurement were performed, but no decrease in adhesiveness or light transmittance was observed in either case. The test results are summarized in Table 1.

Example 2 Cellosolve acetate 100 was added to a 1 L flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel.
Parts by weight were charged and the inside of the flask was purged with nitrogen. 75 parts by weight of N-cyclohexylmaleimide, 45 parts by weight of norbornyl methacrylate (bicyclo[2.2.1]hept-2-yl methacrylate ester), 3 parts by weight of methacrylic acid
0 parts by weight, 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate, and the above 1 liter was dissolved.
The mixture was added dropwise to the flask at 80° C. over 3 hours in a nitrogen stream. After further stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained for 2 hours.

Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd., E
OCN-102S) 50 parts by weight, trimellitic anhydride 1
0 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.; SH-
6040) 1.6 parts by weight, Cellosolve Acetate 375
Parts by weight were added and uniformly mixed and dissolved at room temperature. The resulting solution had a viscosity of 48 centipoise (25°C) and a non-volatile content of 2
It was 0.3% by weight (180°C/1h). The obtained solution was coated on glass in the same manner as in Example 1, cured by heating, and various characteristic tests of the coating film were conducted. The results are shown in Table 1.

Example 3 Cellosolve acetate 100 was added to a 1 L flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel.
Parts by weight were charged and the inside of the flask was purged with nitrogen. 60 parts by weight of N-phenylmaleimide, tricyclo[5] methacrylate
, 2,1,02'6]dec-8-yl ester (Hitachi Chemical Co., Ltd., FA-513M), 30 parts by weight of methacrylic acid, and 0.6 parts by weight of azobisisobutyronitrile were added to cellosolve. The solution was dissolved in 350 parts by weight of acetate and added dropwise to the aforementioned 1 liter flask at 80° C. over 3 hours in a nitrogen stream. After further stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained for 2 hours.

Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd., E
OCN-102S) 70 parts by weight, trimellitic anhydride 1
7.5 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd. SH)
-6040) 1.9 parts by weight, Cellosolve Acetate 45
0 parts by weight was 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 20.8% by weight (180° C. for 1 h). The obtained solution was coated on glass in the same manner as in Example 1, cured by heating, and various characteristic tests of the coating film were conducted. The results are shown in Table 1.

Example 4 Cellosolve acetate 100 was added to a 1 L flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel.
Parts by weight were charged and the inside of the flask was purged with nitrogen. 75 parts by weight of N-phenylmaleimide, tricyclo[5] methacrylate
, 2,1,02'6]dec-8-yl ester (Hitachi Chemical Co., Ltd., FA-513M), 30 parts by weight of methacrylic acid, and 0.6 parts by weight of azobisisobutyronitrile were added to cellosolve. The solution was dissolved in 350 parts by weight of acetate and added dropwise to the aforementioned 1 liter flask at 80° C. over 3 hours in a nitrogen stream. After further stirring at 80°C for 5 hours, the temperature was raised to 120°C and maintained for 2 hours.

Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd., E
OCN-102S) 50 parts by weight, trimellitic anhydride 1
0 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd. SH-6)
040) 1.6 parts by weight 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 43 centipoise (at 25°C) and a non-volatile content of 20
．． It was 1% by weight (180°C for 1h). The obtained solution was coated on glass in the same manner as in Example 1, cured by heating, and various characteristic tests of the coating film were conducted. The results are shown in Table 1.

Comparative Example 1 Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd.)
EOCN-102S) 10 parts by weight, trimellitic anhydride 3 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd. SH-6)
Example 1
In the same manner as above, it was applied onto glass and cured by heating, and various characteristic tests of the coating film were conducted. The results are shown in Table 1.

Comparative Example 2 Polyglycidyl methacrylate (polystyrene equivalent weight average molecular weight approximately 80,000) 6 g, trimellitic anhydride 0
．． 6g, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd. SH-60)
40) Add 0.3 g and 35 parts by weight of cellosolve acetate, mix and dissolve uniformly at room temperature, and use the resulting solution as Example 1.
In the same manner as above, it was applied onto glass and cured by heating, and various characteristic tests of the coating film were conducted. The results are shown in Table 1.

[0051]

[Table 1]

Example 5 The surface hardness of the coating films formed in Examples 1 to 4 was determined by pencil hardness (J
IS K-5400). The results are shown in Table 2.

[0053]

[Table 2]

Example 6 Using the composition solutions prepared in Examples 1 to 4, suitability for color filter substrates was investigated. As a testing method, a color filter base material was prepared using a generally known method, and the applicability on this base material and heat resistance were examined. The color filter base material was first prepared by spin-coating an aqueous solution of gelatin-dichromammonium (10:1, weight ratio) on a transparent glass substrate so that the film thickness after drying was 1 μm, and then coating it at 80°C for 10 minutes.
After drying for minutes, the resulting coating film was irradiated with ultraviolet rays, and then developed with pure water to obtain a dyed substrate layer. This was immersed in the following red dyeing bath, washed with water, and then dried at 150° C. for 30 minutes to form a color filter base material dyed red. Dyeing bath Suminol Milling Red RS (Sumitomo Chemical Co., Ltd.)
(manufactured by) 2g acetic acid

3g distilled water

100g

[0055] Next, the above composition solution is applied on this color filter base material for 2 to 3 hours.
A protective layer was formed by spin coating at 1,000 rpm and drying at 180° C. for 1 hour. Indium tin oxide (ITO) was deposited on the protective layer-equipped color filter thus prepared in accordance with a conventional method, and then patterned by photolithography. The color filter with this ITO pattern was observed in detail with an optical microscope, and no wrinkles or cracks were observed on the color filter or the protective film.
Adhesion was also good.

[0056]

Effects of the Invention As is clear from the examples, the coating film formed by the coating resin composition of the present invention is smooth, has transparency, adhesion, water resistance, chemical resistance, heat resistance, and scratch resistance. It is extremely excellent in the following, and is useful as a coating material for various articles, especially as a color filter protective film material.

Claims (5)

[Claims] [Claim 1] A. (1) N-substituted maleimide, (2)
Alicyclic acrylic ester and/or alicyclic methacrylic ester having an alicyclic structure having 6 to 20 carbon atoms,
(3) acrylic acid and/or methacrylic acid and (4) optionally (1), (2) and/or (3)
A copolymer resin obtained by copolymerizing an unsaturated monomer copolymerizable with B. A coating resin composition comprising an epoxy resin having two or more epoxy groups in the molecule. Claim 2: Furthermore, C. 2. The coating resin composition according to claim 1, comprising at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids. 3. The N-substituted maleimide is N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-substituted maleimide, and N-substituted maleimide.
The coating resin composition according to claim 1 or 2, which is at least one compound selected from the group consisting of butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N-alkyl group-substituted phenylmaleimide. 4. The coating resin composition according to claim 1, wherein the epoxy resin is at least one compound selected from the group consisting of phenol novolac epoxy resins and cresol novolac epoxy resins. 5. A resin composition for a color filter protective film, comprising the coating resin composition according to claim 1, 2, 3, or 4.