JPH061944A - Resin composition for coating and resin composition for color filter protection film produced by using the composition - Google Patents

Abstract

PURPOSE:To provide a coating resin composition having excellent smoothness, transparency, adhesivity, water-resistance, chemical resistance, heat-resistance, scratch resistance and low-temperature curability. CONSTITUTION:The objective coating resin composition contains (A) a copolymer resin produced by copolymerizing (1) an N-substituted maleimide and (2) acrylic acid or methacrylic acid, (B) an epoxy resin having >=2 epoxy groups in the molecule, (C) a tertiary amine compound and, as necessary, (D) a polybasic carboxylic acid anhydride or a polybasic carboxylic acid.

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 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 methacrylate-based resins described in JP-A-60-216307, and JP-A-63-131.
A melamine resin, an epoxy resin, and other polyimide resins described in Japanese Patent Laid-Open No. 103 have been proposed.

[0007]

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

For example, acrylic resins have insufficient heat resistance, and there is a problem that wrinkles and cracks are generated on the surface of the film during the vapor deposition of ITO or the like.

The polyglycidyl methacrylate resin is insufficient in adhesion to a glass substrate or the like, and must sufficiently prevent peeling during the liquid crystal element assembling process and prevent chemicals from entering the color filter layer. I can't.

Although melamine resin has relatively high heat resistance, it has extremely poor adhesion to a glass substrate or a color filter, and is likely to cause cissing on the substrate or filter.

If the epoxy resin has good adhesion, the heat resistance is insufficient, and if the epoxy resin has high heat resistance, the adhesion and coating properties are poor, so that the required properties cannot be balanced. Further, the polyimide resin has problems that it is insufficient in transparency, lacks in storage stability of the varnish, and can use only a solvent for immersing the color filter.

The object of the present invention is to solve the drawbacks of the above-mentioned conventional materials and to achieve a well-balanced and novel new material which can satisfy all the required properties such as heat resistance, chemical resistance, adhesiveness, coating property, transparency and scratch resistance. A resin composition for coating, which can be cured at a low temperature, and a resin composition for a color filter protective film using the same.

[0013]

The coating resin composition in the present invention comprises: A, (1) N-substituted maleimide, and (2) a copolymer resin obtained by copolymerizing acrylic acid or methacrylic acid, B, a molecule. It contains an epoxy resin having two or more epoxy groups, C, and a tertiary amine compound. This coating resin composition is particularly suitable for a color filter protective film resin composition.

As the N-substituted maleimide 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,
At least one selected from the group consisting of N-alkyl group-substituted maleimides such as N-ethylmaleimide, N-propylmaleimide, and N-butylmaleimide, N-cycloalkyl-group-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide and N-alkyl-substituted phenylmaleimide.
From the viewpoint of heat resistance and adhesiveness to a substrate, it is preferable to use a compound of a kind. Of these, N-cyclohexylmaleimide and N-phenylmaleimide are particularly preferable. In the copolymer resin which is the component A

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

(1) N-substituted maleimide or (2) another unsaturated monomer (3) copolymerizable with acrylic acid or methacrylic acid may be used as the monomer component of the copolymer resin of component A. As such an unsaturated monomer,
There are unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds and the like.

Examples of the unsaturated fatty acid ester include methyl acrylate, ethyl acrylate, butyl acrylate,
Acrylic acid alkyl ester such as 2-ethylhexyl acrylate, cyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl acrylate, isobornyl acrylate, norbornyl acrylate and the like cycloalkyl acrylate Ester, phenyl acrylate, aromatic acrylate such as benzyl acrylate, glycidyl acrylate, acrylate such as 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate Methacrylic acid alkyl esters such as, cyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] deca-8-yl, isobornyl methacrylate, norbornyl methacrylate and other cycloalkyl methacrylates Tell, phenyl methacrylate,
There are methacrylic acid aromatic esters such as benzyl methacrylate, glycidyl methacrylate, and methacrylic acid esters such as 2-hydroxyethyl methacrylate.

Examples of the aromatic vinyl compound include styrene and α-methylstyrene, α-ethylstyrene and the like α.
-Substituted styrene, chlorostyrene, vinyltoluene, t
-Nuclear substituted styrene such as butyl styrene.

Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

The (1) N-substituted maleimide, (2) acrylic acid or methacrylic acid and (3) other unsaturated monomers are 20 to 70% by weight and 5 to 30% by weight, respectively, based on the total amount thereof. And 0 to 50% by weight are preferably used so that the total amount becomes 100% by weight.
(1) When the amount of N-substituted maleimide is too small, the heat resistance of the obtained coating film tends to be insufficient, and conversely, when it is too large, the adhesion and coating properties tend to be inconvenient. (2) When the amount of acrylic acid or methacrylic acid is too small, the heat resistance and scratch resistance of the obtained cured product tend to be insufficient, and conversely when it is too large, the coating properties and the chemical resistance of the cured product tend to decrease. There is. (3) If the amount of other unsaturated monomers is too large, the effect of the present invention tends to be insufficient.

These (1) N-substituted maleimides, (2)
In copolymerizing acrylic acid or methacrylic acid and (3) another unsaturated monomer, 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 above-mentioned 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 as 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, usually, when used as a coating resin composition, since it contains a solvent, it is preferable to polymerize by a solution polymerization method using the same solvent, but the polymer is prepared by a method such as methanol reprecipitation method after polymer production. It is also possible to isolate and dissolve in another solvent before use.

The epoxy resin having two or more epoxy groups in the molecule which is the 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 novolac epoxy resin, Cresol novolac epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin,
Although there are heterocyclic epoxy resins and the like, phenol novolac epoxy resin and cresol novolac epoxy resin are particularly preferable in terms of heat resistance and adhesion.

The tertiary amine compound which is the C component in the present invention includes trimethylamine, triethylamine, tributylamine, dimethylethylamine, dimethylpropylamine, methylethylpropylamine, benzyldimethylamine, benzyldiethylamine, pyridine, triethanolamine, N, N'-dimethylethanolamine, N, N'-diethylethanolamine,
2,4,6-tris- (dimethylaminomethyl) phenol and the like. Among them, a C 5-20 tertiary amine compound is preferred because it is less likely to volatilize during heat curing and has a high activity as a curing accelerator.

The coating resin composition of the present invention comprises:
If necessary, various components (D component) can be used in addition to the A component, the B component and the C component. From the viewpoint of improving heat resistance and scratch resistance, it is preferable to use at least one compound selected from the group consisting of polycarboxylic acid anhydrides and polycarboxylic acids as the component D.

The polyvalent carboxylic acid anhydrides include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic 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 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, 30 parts by weight of the component B epoxy resin is added to 100 parts by weight of the component A copolymer resin.
It is preferable to add 300 parts by weight. If the amount of the component B epoxy resin is too small, the chemical resistance tends to be insufficient, and if it is too large, the adhesion tends to decrease. C
The tertiary amine compound as the component is the epoxy resin 1 as the component B.
It is preferable to use 0.01 to 10 parts by weight, especially 0.1 to 5 parts by weight, relative to 00 parts by weight. If the amount of the tertiary amine compound as the component C is too small, it tends to be difficult to cure at low temperature, and if the amount is too large, the coating film tends to have a high degree of deterioration and heat resistance. The polyvalent carboxylic acid anhydride or polyvalent carboxylic acid in the component D is preferably used in the range of 0 to 50 parts by weight with respect to 100 parts by weight of the copolymer resin as the component A. If polycarboxylic acid anhydride or polycarboxylic acid is too much, coating property,
The chemical resistance tends 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 thereof. 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 epoxy 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 formed into a coating film by dissolving it in a solvent and applying it, followed by heating and curing. 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,
If necessary, the composition of the present invention may be added with a curing accelerator used for curing a general epoxy resin, a stabilizer such as an antioxidant or an ultraviolet absorber, etc., to the extent that transparency is not impaired. Good.

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 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 and tough, and has light resistance, heat resistance, water resistance and solvent resistance. 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.

In the prior art, coating properties, adhesion,
Although none of them satisfy all the required properties such as heat resistance, the composition of the present invention can satisfy each of these required properties in a well-balanced manner by combining a compound having a specific structure. Not only this, the compositions of the present invention exhibit excellent low temperature curability, eg, 1
It exhibits sufficiently excellent characteristics even at a curing temperature of 70 ° C or lower. In particular, tertiary amines are superior to other curing accelerators such as phosphines and imidazoles in low temperature curability.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 A 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel was charged with 100 parts by weight of cellosolve acetate (acetoxyethoxyethane), and the inside of the flask was replaced with nitrogen. N-phenylmaleimide 75 parts by weight, methacrylic acid 30 parts by weight, methyl methacrylate 45
Parts by weight and 0.6 parts by weight of azobisisobutyronitrile are dissolved in 350 parts by weight of cellosolve acetate,
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 kept for 2 hours. The obtained copolymer resin solution had a viscosity of 43 poise (25 ° C.) and a nonvolatile content of 25.4 wt% (1
80 ° C, 1h, according to JIS C-2103), acid value 3
It was 2.5 (mgKOH / g).

400 parts by weight of this copolymer resin solution was mixed with cresol novolac epoxy resin [EOCN-102S; trade name of Nippon Kayaku Co., Ltd., epoxy equivalent 214 (g / e).
q), softening point 75 ° C.] 50 parts by weight, trimellitic anhydride 10 parts by weight, benzyldimethylamine 1.0 part by weight, γ
-Glycidoxypropyltrimethoxysilane [SH-6
040; trade name of Toray Dow Corning Silicone Co., Ltd.] 1.6 parts by weight and 375 parts by weight of cellosolve acetate were added and uniformly mixed and dissolved at room temperature. The obtained solution had a viscosity of 57 centipoise (25 ° C.) and a nonvolatile content of 20.2 wt% (180 ° C., 1 h).

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, alkali-free glass) at a rotation speed of 1,000 rpm using a spin coater. 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 2.0 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 the one coated with the absorption spectrum at 400 nm to 800 nm of the coating film was measured as a reference, the light transmittance was 90% or more in the entire region.

A glass plate having 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 at room temperature for 30 minutes (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 250 ° C for 1
The treatment of leaving for a time (hereinafter referred to as 250 ° C. treatment) was performed separately, and after each treatment, the above-described scoring test and measurement of 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 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Example 2 A 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser, and a dropping funnel was charged with 75 parts by weight of cellosolve acetate, and the inside of the flask was replaced with nitrogen. 105 parts by weight of N-phenylmaleimide, 30 parts by weight of methacrylic acid, 45 parts by weight of tricyclo [5.2.1.0 ^2,6 ] dec-8-yl methacrylate, 0.6 part by weight of azobisisobutyronitrile. It was dissolved in 350 parts by weight of cellosolve acetate and added dropwise to the aforementioned 1 liter flask in a nitrogen stream at 80 ° C. over 3 hours. After further stirring at 80 ° C. for 5 hours, 0.3 part by weight of azobisisobutyronitrile was added,
The temperature was raised to 120 ° C. and kept for 2 hours. The obtained copolymer resin solution has a viscosity of 40 poise (25 ° C.), a nonvolatile content of 25.0 wt% (180 ° C., 1 h), and an acid value of 32.9 (m).
gKOH / g).

To 400 parts by weight of this copolymer resin solution, 100 parts by weight of cresol novolac epoxy resin [EOCN-103S; Nippon Kayaku Co., Ltd., epoxy equivalent 218 (g / eq), softening point 85 ° C.], trimellitic anhydride 20 parts by weight, benzyldimethylamine 1.0 part by weight, γ-glycidoxypropyltrimethoxysilane [SH-6040;
Toray Dow Corning Silicone Co., Ltd. product name] 2.
2 parts by weight and 500 parts by weight of cellosolve acetate were added and uniformly mixed and dissolved at room temperature. The obtained solution has a viscosity of 42 centipoise (25 ° C) and a nonvolatile content (180 ° C, 1
h) It was 21.5% by weight. The obtained solution was used in Example 1.
In the same manner as above, coating on glass and heat curing were performed, and various characteristics tests of the coating film were conducted. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Example 3 Cellosolve acetate 100 was added to a 1-liter flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a reflux condenser and a dropping funnel.
Part by weight was charged and the inside of the flask was replaced with nitrogen. 90 parts by weight of N-cyclohexylmaleimide, 30 parts by weight of methacrylic acid, 30 parts by weight of ethyl acrylate, and 0.6 parts by weight of azobisisobutyronitrile were dissolved in 350 parts by weight of cellosolve acetate, and the solution was introduced into a 1 l flask in a nitrogen stream. 80 ° C
Was added dropwise over 3 hours. After further stirring at 80 ° C for 5 hours, the temperature was raised to 120 ° C and kept for 2 hours.

400 parts by weight of the obtained copolymer resin solution was added to cresol novolac epoxy resin [EOCN-102.
S; trade name of Nippon Kayaku Co., Ltd.] 50 parts by weight, trimellitic anhydride 10 parts by weight, benzyldimethylamine 0.5 parts by weight, γ-glycidoxypropyltrimethoxysilane [S
H-6040 Toray Dow Corning Silicone Co., Ltd.
Trade name] 1.6 parts by weight and 375 parts by weight of cellosolve acetate were added and uniformly mixed and dissolved at room temperature. The obtained solution has a viscosity of 71 centipoise (25 ° C) and a nonvolatile content of 2
It was 0.6% by weight (180 ° C., 1 h). The obtained solution was coated on glass and heat-cured in the same manner as in Example 1 to test various characteristics of the coating film. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Comparative Example 1 Cresol novolac epoxy resin (Nippon Kayaku Co., Ltd. E
OCN-103S) 10 parts by weight, trimellitic anhydride 3
Parts by weight, γ-glycidoxypropyltrimethoxysilane (SH-60, Toray Dow Corning Silicone Co., Ltd.)
40) 0.1 parts by weight and 40 parts by weight of cellosolve acetate were uniformly mixed and dissolved at room temperature, and the obtained solution was applied on a glass plate and cured by heating in the same manner as in Example 1 to obtain various characteristics of the coating film. The test was conducted. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Comparative Example 2 The procedure of Example 1 was repeated, except that the effect promoter benzyldimethylamine was not used. Various characteristics tests of the coating film were conducted. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Comparative Example 3 6 g of polyglycidyl methacrylate (weight average molecular weight in terms of polystyrene: about 80,000), 0.6 g of trimellitic anhydride, γ-glycidoxypropyltrimethoxysilane [SH-6040; Toray Dow Corning. Trade name of Silicone Co., Ltd.] 0.3 g, cellosolve acetate 35
Parts by weight were uniformly mixed and dissolved at room temperature, and the obtained solution was coated on glass and cured by heating in the same manner as in Example 1, and various characteristics tests of coating films were conducted. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

Comparative Example 4 The procedure of Example 1 was repeated except that triphenylphosphine was used in place of benzyldimethylamine as the effect accelerator in Example 1. Various characteristics tests of the coating film were conducted. Table 1 shows the results of the goose eye test and Table 2 shows the results of the light transmittance test.

[0052]

[Table 1] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Gobang eye test results (remaining number / 100 ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 250 ℃ 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 Comparative Example 1 100/100 0/100 100 / 100 100/100 100/100 Comparative example 2 100/100 10/100 100/100 50/100 100/100 Comparative example 3 100/100 0/100 100/100 0/100 100/100 Comparative example 4 100/100 0/100 100/100 30/100 100/100 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━

[0053]

[Table 2] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 1 Light transmittance test results (400 to 800 nm ) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Immediately after curing PCT NMP NaOH 250 ℃ After treatment After treatment After treatment After treatment After ─────────────────────────────────── Example 1 90% or more 90% or more 90% or more 90% 90% or more Example 2 90% or more 90% or more 90% or more 90% or more 90% or more Example 3 90% or more 90% or more 90% or more 90% or more 90% or more Comparative Example 1 90% or more 90% or more 90 80% 90% or more Comparative Example 2 90% or more 90% or more 90% or more 80% 90% or more Comparative Example 3 90% or more 90% or more 80% 50% or less 90% or more Comparative Example 4 90% or more 90% or more 90% or more 80% 90% or more ━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━━

Comparative Example 5 The procedure of Example 1 was repeated except that 2-ethyl-4-methylimidazole was used in place of benzyldimethylamine which was an effect accelerator in Example 1, and the various properties of the coating film were not tested. A composition solution of This composition solution is 2
-Ethyl-4-methylimidazole did not dissolve and was cloudy.

The following tests were further conducted using the coating films formed in Examples 1 to 3 and Comparative Examples 1 to 4. Test Example The coating films formed in Examples 1 to 3 and Comparative Examples 1 to 4 are 250
After left in a gear oven at ℃ for 1 hour, measure the film thickness,
Reduction rate of film thickness [(film thickness after test / film thickness before test) × 10
0%] was calculated. The results are shown in Table 3.

[Table 3] ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Table 2 Reduction rate of film thickness ━━━ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ Example 1 0.5% Example 2 0.6% Example 3 0.8% Comparative Example 1 5.0% Comparative Example 2 3.0% Comparative Example 3 7.5% Comparative Example 4 2.5% ━━━━━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━

Example 4 The composition solutions prepared in Examples 1 to 3 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 was prepared by first spin-coating a transparent glass substrate with an aqueous solution of gelatin-ammonium dichromate (10: 1, weight ratio) so that the film thickness after drying was 1 μm, and then at 80 ° C. for 1 hour.
After being dried for 0 minutes, the resulting coating film was irradiated with ultraviolet rays and then developed with pure water to obtain a dyed substrate layer. This is immersed in a red dyeing bath of the following composition, washed with water, and then at 150 ° C. for 30 minutes.
A color filter substrate dyed red was formed by drying for a minute. Composition of dyeing bath Suminol Milling Red RS (Sumitomo Chemical Co., Ltd.) 2g Acetic acid 3g Distilled water 100g

Next, the composition solution was spin-coated on this color filter substrate at 2,000 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 on the color filter or the protective film, and the adhesiveness and adhesion between the color filter and the protective film were good. It was

[0058]

The coating resin composition according to claim 1 or 2 can be cured at a low temperature, and the coating film formed from the composition is smooth and has transparency, adhesiveness and water resistance. Excellent in chemical resistance, heat resistance and scratch resistance. The resin composition for a color filter protective film according to claim 3 contains the resin composition for coating according to claim 1 or 2, is useful as a color filter protective film, and is the same as the above resin composition. Have an effect.

Claims (3)

[Claims] 1. A copolymer resin obtained by copolymerizing A, (1) N-substituted maleimide, and (2) acrylic acid or methacrylic acid, B, an epoxy resin having two or more epoxy groups in the molecule, and C, A coating resin composition containing a tertiary amine compound. 2. Further, at least one selected from the group consisting of D, polycarboxylic acid anhydride and polycarboxylic acid.
The coating resin composition according to claim 1, which comprises one kind of compound. 3. A resin composition for a color filter protective film, comprising the coating resin composition according to claim 1 or 2.