JPH06145595A - Curable coating resin composition and resin composition containing the same for forming protective film for color filter - Google Patents

Abstract

PURPOSE:To obtain a curable coating resin compsn. which gives a smooth coating film excellent in transparency, ahdesiveness, and resistances to moisture, chemicals, heat, and scratch by compounding two specific acrylic copolymers. CONSTITUTION:A coating resin compsn. contains a copolymer resin obtd. by copolymerizing a monomer mixture contg. an N-substd. maleimide and glycidyl (meth)acrylate and a copolymer resin obtd. by copolymerizing a monomer mixture contg. an N-substd. maleimide and (meth)acrylic acid. The compsn. gives a smooth coating film excellent in transparency, adhesiveness and resistances to moisture, chemicals, heat, and scratch and is suitably used as a resin compsn. for protecting a color filter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable coating resin composition and a color filter protective film resin composition using the same.

[0002]

2. Description of the Related Art A coating film is often formed for the purpose of preventing deterioration and damage of the surface of various articles. In such coating film, a smooth coating film can be obtained, high adhesion to the substrate, toughness, excellent water resistance, chemical resistance, solvent resistance, heat resistance In addition, it is required to have performance such as high light resistance and no deterioration for a long period of time.

In recent years, liquid crystal display devices, solar cells,
As a coating film used for optical disks and the like, applications requiring transparency and the like in addition to the above-mentioned performance are increasing.

For example, in recent years, various color liquid crystal display devices incorporating a color filter have been announced. In the production of 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) or the like is vapor-deposited thereon, and a transparent electrode is formed by patterning by a photolithography method. After the formation, a method of disposing liquid crystal on the liquid crystal is becoming mainstream. In this case, the color filter does not have sufficient heat resistance and chemical resistance to withstand the process of depositing ITO on the color filter and forming the transparent electrode by the photolithography method. 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 a glass substrate or a color filter, coating properties, transparency, and scratch resistance. Of these, heat resistance is
When forming a transparent electrode such as O by vapor deposition, the surface of the protective film is usually heated to 200 ° C. or higher, and therefore it is necessary that the surface is stable under these conditions.

As a coating material having such excellent heat resistance and chemical resistance, there is disclosed in Japanese Patent Laid-Open No. 58-196506.
Acrylic resins described in JP-A-62-119501, polyglycidyl (meth) acrylate-based resins described in JP-A-60-216307, and JP-A-63-
A melamine resin, an epoxy resin, and other polyimide resins described in Japanese Patent No. 131103 have been proposed.

However, the materials proposed hitherto have respective drawbacks, and there is no well-balanced material satisfying all the required characteristics.

[0008]

The present invention solves the above-mentioned drawbacks of conventional materials and satisfies all the required properties such as heat resistance, chemical resistance, adhesiveness, coating property, transparency and scratch resistance. The present invention provides a novel curable coating resin composition that is well-balanced and that can be cured at low temperature, and a resin composition for a color filter protective film using the same.

[0009]

The curable coating resin composition of the present invention comprises a copolymer resin containing (1) N-substituted maleimide and (2) glycidyl methacrylate or glycidyl acrylate as essential components, and B. (3) N-substituted maleimide and (4) a copolymer resin containing acrylic acid or methacrylic acid as essential components. This curable coating resin composition is particularly suitable for a color filter protective film resin composition.

As the N-substituted maleimide (1) as a monomer component constituting the copolymer resin which is the component A in the present invention, known ones can be used, but N-methylmaleimide, N-ethylmaleimide, N- At least one selected from the group consisting of N-alkyl group-substituted maleimides such as propylmaleimide and N-butylmaleimide, N-cycloalkyl group-substituted maleimides such as N-cyclohexylmaleimide, and N-aryl group-substituted maleimides such as N-phenylmaleimide. A variety of compounds can be used.
Among these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferable.

(2) Two or more kinds of glycidyl methacrylate or glycidyl acrylic acid may be used in combination.

The copolymer resin as the component A in the present invention may contain other copolymerizable unsaturated monomer in addition to the components (1) and (2) as a monomer constituting the copolymer resin. Good. Examples of such compounds include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds and the like.

As the unsaturated fatty acid ester, the component (2) is excluded, and an alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or an acryl such as cyclohexyl acrylate is used. Acid cycloalkyl ester, phenyl acrylate, acrylic acid aromatic ester such as benzyl acrylate, norbornyl acrylate, norbornyl methyl acrylate, adamantyl acrylate, tricyclo acrylate [5.2.1.0 ^2,6 ] Tertiary in the ring such as decan-8-yl, tricyclo [5.2.1.0 ^2,6 ] decan-3 (or 4) -ylmethyl acrylate, bornyl acrylate, isobornyl acrylate, methylcyclohexyl methacrylate, etc. Contains carbon and has 7 to 2 carbon atoms
Acrylic ester having an alicyclic group of 0 bonded to an ester group, acrylic ester such as 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, etc. Of methacrylic acid alkyl ester, methacrylic acid cycloalkyl ester such as cyclohexyl methacrylate, phenyl methacrylate, aromatic methacrylic acid ester such as benzyl methacrylate, norbornyl methacrylate, norbornyl methyl methacrylate, adamantyl methacrylate, tricyclo methacrylate. [5.2.
1.0 ^2,6 ] Decan-8-yl, tricyclo [5.2.1.0 ^2,6 ] decan-3 (or 4) -ylmethyl methacrylate, bornyl methacrylate, isobornyl methacrylate, methylcyclohexyl methacrylate Methacrylic acid ester, such as methacrylic acid ester, in which an alicyclic group having a carbon number of 7 to 20 is bonded to the ester group and contains tertiary carbon in the ring.

Examples of the aromatic vinyl compound include styrene or α-substituted styrene such as α-methylstyrene and α-ethylstyrene, chlorostyrene, vinyltoluene,
Nuclear substituted styrenes such as t-butylstyrene are available.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.

Each of the above-mentioned monomers, based on the total amount thereof, contains 30 to 70% by weight of the component (1), 30 to 60% by weight of the component (2), and other copolymerizable unsaturated monomer. It is preferable to use it in a ratio within the range of 0 to 40% by weight of body components. If the amount of component (1) is too small, the adhesion of the resulting coating film tends to decrease, and if it is too large, the heat resistance tends to decrease. If the amount of component (2) is too small, the heat resistance of the resulting coating film tends to decrease, and if it is too large, the adhesion tends to decrease. If the amount of other copolymerizable unsaturated monomer is too large, the effect of the present invention may be insufficient.

The copolymer resin as the component A is produced by blending the above-mentioned monomers (1), (2) and other copolymerizable unsaturated monomer components and copolymerizing them. can do. Known methods such as radical polymerization and ionic polymerization can be used. For example, it can be produced by a method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method in the presence of a polymerization initiator.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydrophthalate and t-butylperoxy-2.
-Ethyl hexanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane and other organic peroxides, azobisisobutyronitrile, azobis-
Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl, water-soluble catalysts represented by potassium persulfate and ammonium persulfate, and peroxides or persulfates. Any redox catalyst that can be used in ordinary radical polymerization, such as a redox catalyst obtained by combining a solvent and a reducing agent, can be used. The polymerization catalyst is preferably used in the range of 0.01 to 10% by weight based on the total amount of the above monomers.

Further, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer and the like can be added as a polymerization regulator, if necessary, for controlling the molecular weight.

The polymerization temperature is preferably selected in the range of 0 to 200 ° C, particularly preferably 50 to 120 ° C.

As the solvent in the solution polymerization, the solvent 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, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ether solvents such as 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 glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Examples include ester solvents such as γ-butyrolactone; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these solvents,
Ester solvent and ketone solvent are preferred, alone,
Alternatively, two or more kinds can be mixed and used.
In addition, normally, when used as a coating resin composition, it is preferable to polymerize by a solution polymerization method using the same solvent because it contains a solvent. It is also possible to isolate and dissolve in another solvent before use.

The molecular weight of the copolymer resin as the component A is not particularly limited, but is preferably 5,000 to 300,000 (weight average molecular weight in terms of standard polystyrene), and the film thickness of the coating film to be formed, It is appropriately determined in consideration of the target conditions for coating film formation such as the coating method.

The (3) N-substituted maleimide as a monomer component constituting the copolymer resin which is the B component in the present invention can be the N-substituted maleimide which is a component of the above-mentioned copolymer resin which is the A component. Can be used. The use of this component is preferable from the viewpoints of heat resistance and adhesion to the substrate. Particularly preferred N-substituted maleimides are N-cyclohexylmaleimide and N-phenylmaleimide.

When (4) acrylic acid or methacrylic acid is used, these may be used together.

Other than (3) N-substituted maleimide and (4) acrylic acid or methacrylic acid, other copolymerizable unsaturated monomers may be used as the monomer component of the component B copolymer resin. Such unsaturated monomers include unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds and the like. Specific examples of these include other copolymers as the monomer component of the B component copolymer resin. The thing which was illustrated as a polymerizable unsaturated monomer can be mentioned.

As the unsaturated fatty acid ester, there is an unsaturated fatty acid ester which can be a component of the above-mentioned component A copolymer resin, and methacrylic acid glycidyl ester or acrylic acid glycidyl ester may be used.

As the aromatic vinyl compound, there is an aromatic vinyl compound which can be a component of the above-mentioned component A copolymer resin.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

Each of the above-mentioned monomers, based on the total amount thereof, contains 20 to 70% by weight of the component (3), 5 to 30% by weight of the component (4) and 0 to other unsaturated monomers. It is preferably used in a proportion within the range of 50% by weight. If the component (3) is too small, the heat resistance of the resulting coating film tends to be insufficient, and conversely, if it is too large, the adhesion and coating properties tend to be inconvenient. If the component (4) is too small, the heat resistance and scratch resistance of the resulting cured product will tend to be insufficient, and conversely, if it is too large, the coating properties and the chemical resistance of the cured product will tend to decrease. If the amount of other unsaturated monomers is too large, the effect of the present invention tends to be insufficient.

The copolymer resin as the component B is produced by blending the respective monomers of the above-mentioned component (3), the component (4) and the other copolymerizable unsaturated monomer component and copolymerizing them. can do. In this case, the polymerization method, the usable polymerization initiator, the polymerization regulator, the polymerization temperature, and the solvent in the solution polymerization are the same as in the case of the copolymer resin as the component A.

The curable resin composition for coating of the present invention may optionally contain various components (component C) in addition to the components A and B. From the viewpoint of improving heat resistance and chemical resistance, it is preferable to use at least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the C component.

Examples of the polyvalent carboxylic acid anhydrides include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride,
Aliphatic dicarboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride and methylendomethylenetetrahydrophthalic anhydride; Fats such as cyclopentanetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Group polycarboxylic acid dianhydrides; aromatics such as phthalic anhydride, trimetic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Polyhydric carboxylic acid anhydrides; ester group-containing acid anhydrides such as ethylene glycol bis trimellitate and glycerin tris trimellitate can be mentioned. Examples of the polycarboxylic acid 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. Acid, terephthalic acid, isophthalic acid, trimellitic acid,
Examples thereof include aromatic polyvalent carboxylic acids such as pyromellitic acid and benzophenonetetracarboxylic acid.

The polyvalent carboxylic acid anhydride and the polyvalent carboxylic acid may be used alone or in combination of two or more. From the viewpoint of heat resistance, aromatic polycarboxylic acid anhydrides and aromatic polycarboxylic acids are preferable from the viewpoint of heat resistance, and trimellitic anhydride is particularly preferable from the viewpoint of the balance between heat resistance and solubility in solvents.

In the composition of the present invention, 100 to 100 parts by weight of the component A copolymer resin is used, and the component B copolymer resin 30 to 3 is used.
It is preferable to add 00 parts by weight. If the amount of the component B copolymer resin is too small, the adhesion tends to decrease, and if it is too large, the chemical resistance tends to decrease. At least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the component C is preferably used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the copolymer resin as the component B. . If the amount of polyvalent carboxylic acid anhydride or polyvalent carboxylic acid is too large, the coating properties, chemical resistance, etc. tend to decrease. In order to exert the effect of use, it is preferable to use 5 parts by weight or more.

A coupling agent may be added to the composition of the present invention in order to improve the adhesion. The coupling agent is preferably a functional silane coupling agent vinyl group, methacryloyl group, hydroxyl group, carboxyl group, amino group, isocyanate group,
A silane coupling agent having a reactive substituent such as an epoxy group, specifically vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glyce. Examples thereof include sidoxypropyltrimethoxysilane and the like. Particularly, a silane coupling agent having an epoxy group is preferable because it has excellent adhesiveness 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 preferably in the range of 0 to 10 parts by weight when the total amount of the component A copolymer resin and the component B copolymer resin is 100 parts by weight. If it is too much, the chemical resistance tends to decrease. Further, in order to exert the effect of use, it is preferable to use 0.1 part by weight or more.

The composition of the present invention can be usually 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. Specific examples thereof include the solvents exemplified as the solvent for solution polymerization of the copolymer resin which is the component A of the present invention. Of these solvents, ester solvents and ketone solvents are preferable, and they can be used alone or in admixture of two or more.

The method of dissolving the composition of the present invention in a solvent to prepare a composition solution is not particularly limited, and all components may be dissolved in a solvent at the same time to prepare a composition solution. If necessary, two or more solutions may be prepared for each component, and these may be mixed at the time of use to form a composition solution. When the composition solution is prepared as described above, the amount of the solvent used is preferably 50 to 95% by weight of the total amount of the final composition solution used for coating. If it is less than 50% by weight, the solid content concentration is too high, and the leveling property of the coating film may be lowered, or the transparency of the coating film may be reduced, while if it exceeds 95% by weight, the solid content concentration is too low. Therefore, the chemical resistance of the coating film may be insufficient. Also,
In the composition of the present invention, if necessary, an epoxy resin such as epibis type or novolac type, a carboxyl group-containing polymer compound, a curing accelerator used for curing the epoxy resin, an antioxidant or an ultraviolet absorber, etc. Stabilizers and the like may be added.

The method of applying the composition solution of the present invention is not particularly limited, and may include a dipping method, a spray method, a roll coating method, a spin coating method and the like, as well as a coating method such as screen printing and offset printing. is there. The heat curing conditions for the composition of the present invention are appropriately selected depending on the specific type of each component of the composition, the compounding ratio, etc., but are usually 0.1 at 50 to 300 ° C.
-10 hours, preferably 1 to 5 hours at 100 to 250 ° C.

The coating film formed from the composition of the present invention exhibits excellent adhesion to various materials such as glass, metal and plastic, and is smooth, tough, light resistant, heat resistant, water resistant and solvent resistant. Since it has excellent properties and transparency, it is useful as a coating film for various articles. In particular, as a color filter protective film, a surface protective layer or a dye protective layer of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resin with a dye or coloring by dispersing a pigment. Is useful as When it is used as a color filter protective film, it can be appropriately applied and used so that the film thickness after heat curing is 0.05 to 30 μm, preferably 0.1 to 10 μm.

According to the studies of the present inventors, the conventional technique using a polyglycidyl (meth) acrylate resin is to react this resin with a low molecular weight polyvalent carboxylic anhydride or polyvalent carboxylic acid. It was found that the obtained coating film was too fragile and had poor adhesion, and that the number of ester bonds involved in crosslinking was too large and therefore had poor alkali resistance. Further, in the prior art, none of the properties satisfying all the required properties such as coating property, adhesiveness, and heat resistance were satisfied, but the composition of the present invention can meet each of these requirements by combining compounds having a specific structure. It is possible to satisfy the characteristics in good balance.

[0041]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 (Production of Copolymer Resin Solution A-1) 260 parts by weight of cellosolve acetate (acetoxyethoxyethane) was placed in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introducing tube, reflux condenser and dropping funnel. The inside of the charged flask was replaced with nitrogen. N-phenylmaleimide 84
Parts by weight, 116 parts by weight of glycidyl methacrylate and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 100 parts by weight of cellosolve acetate, and added dropwise to the above-mentioned 1 liter flask at 90 ° C. over 3 hours in a nitrogen stream. After further stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 40 parts by weight of cellosolve acetate was added, and then the temperature was raised to 120 ° C. and kept for 2 hours. The obtained copolymer resin solution had a viscosity of 770 poise (25 ° C.), and this copolymer resin was subjected to HLC analysis (G
In PC mode, the column was Gelpack A-120 + Gelpack A-140 + Gelpack A-150, the eluent was tetrahydrofuran, and the detector was a differential refractometer.) The weight average molecular weight in terms of standard polystyrene was about 95,000.

Production Example 2 (Production of Copolymer Resin Solution A-2) In Production Example 1, 84 parts by weight of N-phenylmaleimide and 116 parts by weight of glycidyl methacrylate were added to 120 parts by weight of N-phenylmaleimide and 80 parts by weight of glycidyl methacrylate. It was carried out according to Production Example 1 except that the parts were used.
The viscosity of the obtained copolymer resin solution was 980 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 120,000.

Production Example 3 (Production of Copolymer Resin Solution A-3) According to Production Example 1, except that 84 parts by weight of N-cyclohexylmaleimide was used in place of 84 parts by weight of N-phenylmaleimide in Production Example 1. I went. The viscosity of the obtained copolymer resin solution was 650 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 87,000.

Production Example 4 (Production of Copolymer Resin Solution A-4) In Production Example 1, 84 parts by weight of N-phenylmaleimide and 116 parts by weight of glycidyl methacrylate were replaced by N-.
The procedure of Production Example 1 was repeated except that 120 parts by weight of cyclohexylmaleimide and 80 parts by weight of glycidyl methacrylate were used. The viscosity of the obtained copolymer resin solution is 750.
Centipoise (25 ° C), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene is about 97,000.
It was 0.

Production Example 5 (Production of Copolymer Resin Solution B-1) 150 parts by weight of cellosolve acetate (acetoxyethoxyethane) in a 1 liter flask equipped with a stirrer, thermometer, nitrogen introducing tube, reflux condenser and dropping funnel. The inside of the charged flask was replaced with nitrogen. N-phenylmaleimide 14
0 parts by weight, 40 parts by weight of methacrylic acid, 20 parts by weight of ethyl acrylate and 3.0 parts by weight of azobisisobutyronitrile were dissolved in 300 parts by weight of cellosolve acetate, and the above-mentioned 1 liter flask was heated at 90 ° C. in a nitrogen stream at 90 ° C. It was added dropwise over 3 hours. After further stirring at 90 ° C. for 1 hour, a solution of 0.2 parts by weight of azobisisobutyronitrile dissolved in 16.7 parts by weight of cellosolve acetate was added, and then the temperature was raised to 120 ° C. and maintained for 2 hours. The viscosity of the obtained copolymer resin solution was 560 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene (analyzed by the same method as in Production Example 1) was about 2.
It was 2,000.

Production Example 6 (Production of Copolymer Resin Solution B-2) Except that in Production Example 5, the monomers used were 120 parts by weight of N-cyclomaleimide, 40 parts by weight of methacrylic acid and 40 parts by weight of methyl methacrylate. Was carried out according to Production Example 5. The viscosity of the obtained copolymer resin solution was 480 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 20,000.
Met.

Production Example 7 (Production of Copolymer Resin Solution B-3) In Production Example 5, the monomers used were 100 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid and tricyclomethacrylate [5.2.1. 0 ^2,6 ] decane-8
-Ill It was carried out according to Production Example 5 except that the amount was 60 parts by weight. The viscosity of the obtained copolymer resin solution was 350 centipoise (25 ° C.), and the weight average molecular weight of the obtained copolymer resin in terms of standard polystyrene was about 12,000.

Examples 1 to 12 Copolymer resin solutions A-1 to 100 parts by weight, copolymer resin solutions B-1 to 111 parts by weight, trimellitic anhydride 6.7 parts by weight, γ-glycidoxypropyl 0.7 parts by weight of trimethoxysilane [SH-6040; trade name of Toray Dow Corning Silicone Co., Ltd.], 140.7 parts by weight of cellosolve acetate, 88.9 of diethylene glycol.
Parts by weight were added and uniformly mixed and dissolved at room temperature. Table 1 shows combinations of the copolymer resin solutions A-1 to A-4 and the copolymer resin solutions B-1 to B-3.

This solution was filtered through a membrane filter having a pore size of 0.2 μm, and then spin-coated on a glass plate (Dow Corning 7059 material, non-alkali glass) using a spin coater at 1,000 rpm. After coating, heat the glass plate in a constant temperature bath at 160 ° C for 1 hour,
The coating was cured. The surface of the obtained coating film was extremely smooth, and pinholes and the like were not observed at all. The film thickness measured by a stylus type film thickness meter [Surfcom; trade name of Tokyo Seimitsu Co., Ltd.] was 1.3 to 1.6 μm.

The following tests were conducted on the coating film thus produced. In order to examine the adhesion of the coating film to the glass plate, a tape-like test by peeling the tape (JIS-K-54
00) was performed. As a result, the remaining number was 100/100, and peeling was not observed at all.

Next, when the same glass plate as that coated with the absorption spectrum at 400 nm to 800 nm of the coating film was measured as a reference, the light transmittance was 95% or more in the entire region.

A glass plate provided with this coating film was subjected to a pressure cooker test (120 ° C., 2 atm) for 10 hours (hereinafter referred to as PCT treatment) and immersed in N-methylpyrrolidone for 30 minutes at room temperature (hereinafter referred to as NMP treatment). 5%)
Aqueous sodium hydroxide solution (hereinafter referred to as NaOH treatment)
Soak for 30 minutes at room temperature in a oven at 280 ° C for 1
The treatments that were left for a time (hereinafter referred to as 280 ° C. treatment) were separately performed, and after each treatment, the above-mentioned goggles test and the measurement of the light transmittance were performed. When these results were compared with the test results immediately after coating film production (immediately after curing), adhesiveness and light transmittance were good in all cases. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.

Comparative Example 1 Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd. E
OCN-103S) 100 parts by weight, trimellitic anhydride 30 parts by weight, γ-glycidoxypropyltrimethoxysilane (Toray Dow Corning Silicone SH-
6040) 1.0 part by weight, cellosolve acetate 400
Parts by weight were uniformly mixed and dissolved at room temperature, and the obtained solution was applied onto a glass plate and cured by heating in the same manner as in Examples, and various characteristics tests of coating films were conducted. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.

Comparative Example 2 100 parts by weight of glycidyl polymethacrylate (weight average molecular weight in terms of standard polystyrene of about 80,000), 10 parts by weight of trimellitic anhydride, γ-glycidoxypropyltrimethoxysilane [SH-6040; Toray -Dow Corning Silicone Co., Ltd. trade name] 1.0 parts by weight and 580 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, and the obtained solution was applied onto glass and cured by heating in the same manner as in the example. Then, various characteristics tests of the coating film were conducted. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.

Comparative Example 3 100 parts by weight of copolymer resin solution A-1, 7 parts by weight of trimellitic anhydride, γ-glycidoxypropyltrimethoxysilane [SH-6040; trade name of Toray Dow Corning Silicone Co., Ltd.] ] 0.4 parts by weight, 47 parts by weight of cellosolve acetate, and 49 parts by weight of diethylene glycol were uniformly mixed and dissolved at room temperature, and the obtained solution was applied on glass and cured by heating in the same manner as in Examples to form a coating film. Various characteristic tests were conducted. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.

Comparative Example 4 100 parts by weight of copolymer resin solution B-3, cresol novolac epoxy resin (EOCN-103, manufactured by Nippon Kayaku Co., Ltd.)
S) 30 parts by weight, trimellitic anhydride 6 parts by weight, γ-glycidoxypropyltrimethoxysilane [SH-604
0; Toray Dow Corning Silicone Co., Ltd. product name]
0.7 parts by weight, 70 parts by weight of cellosolve acetate, and 60 parts by weight of diethylene glycol were uniformly mixed and dissolved at room temperature, and the obtained solution was coated on glass and heat-cured in the same manner as in Examples to prepare various coating films. A characteristic test was conducted. Table 2 shows the results of the goose eye test and Table 3 shows the results of the light transmittance test.

[0058]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Combination of copolymer resin solutions A and B ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Copolymer resin solution A Copolymer resin solution B ───── ────────────────────────────── Example 1 A-1 B-1 Example 2 A-1 B-2 Example 3 A-1 B-3 Example 4 A-2 B-1 Example 5 A-2 B-2 Example 6 A-2 B-3 Example 7 A-3 B-1 Example 8 A-3 B -2 Example 9 A-3 B-3 Example 10 A-4 B-1 Example 11 A-4 B-2 Example 12 A-4 B-3 ━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

[0059]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Gobang eye test results (remaining number / 100 ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 100/100 100/100 100/100 100 / 100 100/100 Example 2 100/100 100/100 100/100 100/100 100/100 Example 3 100/100 100/100 100/100 100/100 100/100 Example 4 100/100 100/100 100 / 100 100/100 100/100 Example 5 100/100 100/100 100/100 100/100 100/100 Example 6 100/100 100/100 100/100 100/100 100/100 Example 7 100/100 100/100 100/100 100/100 100/100 Example 8 100/100 100/100 100/100 100/100 100/100 Example 9 100/100 100/100 100/100 100/100 100/100 Example 10 100/100 100/100 10 0/100 100/100 100/100 Example 11 100/100 100/100 100/100 100/100 100/100 Example 12 100/100 100/100 100/100 100/100 100/100 Comparative Example 1 100 / 100 0/100 100/100 100/100 100/100 Comparative example 2 100/100 0/100 100/100 0/100 100/100 Comparative example 3 100/100 0/100 100/100 0/100 100/100 Comparative Example 4 100/100 90/100 100/100 100/100 100/100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━

[0060]

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 3 Light transmittance test results (400 to 800 nm ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 280 ℃ After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 95% or more 95% or more 95% or more 95% 95% or more Example 2 95% or more 95% or more 95% or more 95% or more 95% or more Example 3 95% or more 95% or more 95% or more 95% or more 95% or more Example 4 95% or more 95% or more 95 Example 5 95% or more 95% or more 95% or more 95% or more 95% or more 95% or more Example 6 95% or more 95% or more 95% or more 95% or more 95% or more Example 7 95% or more 95% or more 95% or more 95% or more 95% or more Example 8 95% or more 95% or more 95% or more 95% or more 95% or more Example 9 95% or more 95% or more 95% or more 95% or more 95% or more Example 10 95% or more 95% or more 95% or more 95% or more 95% or more Example 11 95% or more 95% or more 95% or more 95% or more 95% or more Example 12 95% or more 95% or more 95% or more 95% or more 95% or more Comparative Example 1 95% or more 95% or more 90% or more 80% 60 Comparative Example 2 95% or more 50% or less 80% 50% 95% or more Comparative Example 3 95% or more 80% 95% or more 80% 95% or more Comparative Example 4 95% or more 95% or more 95% or more 95% or more 50% or less ━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━━━━

Test Example The composition solutions prepared in Examples 1 to 12 and Comparative Examples 1 to 4 were used to examine suitability for color filter substrates. As a test method, a color filter substrate was prepared by a generally known method, and the coating property and heat resistance on this substrate were examined.
The color filter substrate is prepared by first gelatin-ammonium dichromate (10: 1, weight ratio) on a transparent glass substrate.
After spin-coating the aqueous solution of to give a film thickness after drying of 1 μm, it is dried at 80 ° C. for 10 minutes, the resulting coating film is irradiated with ultraviolet rays and then developed with pure water to give a dyed substrate layer. Got This was immersed in a red dye bath having the following composition, washed with water, and dried at 150 ° C. for 30 minutes to form a color filter substrate dyed red. Composition of dyeing bath Suminol Milling Red RS (Sumitomo Chemical Co., Ltd.) 2g Acetic acid 3g Distilled water 100g

Then, the composition solution was spin-coated on this color filter substrate at 1,000 rpm and dried at 180 ° C. for 1 hour to form a protective layer. Indium tin oxide (ITO) was vapor-deposited on the thus-prepared color filter with a protective film by a conventional method, and then patterned by photolithography. The color filter having this ITO pattern was observed in detail with an optical microscope, but no wrinkles or cracks were observed in the color filter or the protective film produced using the compositions of Examples 1 to 12, and Adhesiveness with protective film,
The adhesion was also good as shown in Table 4.

[0063]

[Table 4] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 4 Color filter substrate proper test results ━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Composition Color filter after ITO deposition Adhesion with surface condition ─── ──────────────────────────────── Example 1 〇 〇 Example 2 〇 〇 Example 3 〇 〇 Example 4 ○ △ Example 5 ○ ○ ○ Example 6 ○ ○ ○ Example 7 ○ ○ ○ Example 8 ○ ○ Example 9 ○ ○ Example 10 ○ △ Example 11 ○ ○ Example 12 ○ ○ Comparative Example 1 ○ × Comparative Example 2 × × Comparative Example 3 ○ × Comparative Example 4 ○ × ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ , The surface condition after ITO deposition should be normal. ◯, wrinkles and cracks were taken as x, adhesion to the color filter was not peeled in the gonan eye test ◯, partially peeled was △, completely peeled was x .

[0064]

EFFECT OF THE INVENTION In the curable resin composition for coating according to claim 1 or 2, the coating film formed from the composition is smooth and has transparency, adhesiveness, moisture resistance, chemical resistance,
It has excellent heat resistance and scratch resistance. The color filter protective film resin composition according to claim 3 contains the curable coating resin composition according to claim 1 or 2, and is useful as a color filter protective film. It has the same effect as the composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // G02F 1/1335 505 7408-2K

Claims (3)

[Claims] 1. A. (1) N-substituted maleimide and (2) copolymer resin containing methacrylic acid glycidyl ester or acrylic acid glycidyl ester as essential components, and B. A curable resin composition for coating comprising (3) N-substituted maleimide and (4) a copolymer resin containing acrylic acid or methacrylic acid as essential components. 2. Further, at least one selected from the group consisting of C, a polycarboxylic acid anhydride and a polycarboxylic acid.
The curable resin composition for coating according to claim 1 or 2, which contains one kind of compound. 3. A resin composition for a color filter protective film, comprising the curable coating resin composition according to claim 1 or 2.