JPH10212448A - Resin composition for cured coating film, color filter-protecting film using the same, color filter and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a copolymer comprising specific monomer components, a polybasic carboxylic acid (anhydride) and a functional silane coupling agent as essential components, excellent in coatability and storage stability, and capable of being used for producing color filter-protecting films. SOLUTION: This resin composition comprises (A) 100 pts.wt. of a copolymer, (B) 5-50 pts.wt. of at least one kind of compound selected from the group consisting of polybasic carboxylic acid anhydrides and polybasic carboxylic acids, and (C) 30-100 pts.wt. of a functional silane coupling agent. The component A comprises (i) 10-45wt.% of an N-substituted maleimide, (ii) 55-60wt.% of glycidyl (meth)acrylate ester and (iii) 0-30wt.% of an unsaturated monomer capable of being copolymerized with the components i and ii. Coating films remarkably improved in isopropyl alcohol(IPA) vapor resistance can thereby be produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for a cured coating film, a color filter protective film using the same, a color filter, and a liquid crystal display device.

[0002]

2. Description of the Related Art In recent years, various color liquid crystal display devices incorporating a color filter have been announced. In manufacturing this color liquid crystal display device, a color filter is provided on a transparent substrate such as glass, and an inorganic thin film made of indium tin oxide (ITO) is deposited thereon, and patterned by photolithography to form a transparent electrode. After forming a liquid crystal, a method of further disposing a liquid crystal thereon has become mainstream. In this case, the color filter has an IT
Since it does not have heat resistance and chemical resistance enough to withstand the process of depositing O and forming a transparent electrode by photolithography, a protective film is formed on the color filter before depositing ITO. There is a need.

The properties required for the color filter protective film include heat resistance, chemical resistance, adhesion to glass substrates and color filters, coating properties, transparency, scratch resistance, and the like. Among them, heat resistance is IT
When a transparent electrode of O or the like is formed by vapor deposition, the surface of the protective film is usually heated to 200 ° C. or higher, so that it is necessary to be stable under this condition. In addition, as for chemical resistance, N.sub.2 which is used for a liquid crystal material or a solvent of a varnish for an alignment film is usually used.
-It must be free from methylpyrrolidone (NMP).

[0004] In recent years, isopropyl alcohol (IPA) has been used in place of the chlorofluorocarbon cleaning agent used in the cleaning process. That is, in the cleaning using the IPA, first, when forming the color filter, the protective film, the ITO, etc., the substrate is washed with water, and then the substrate is washed with an IPA solution at normal temperature.
This is a method of performing a cleaning treatment using IPA vapor under the conditions of (° C.).

[0005] However, although the conventional protective film has resistance to a chlorofluorocarbon cleaning agent, it has low resistance to IPA vapor. Therefore, after patterning the ITO film formed on the protective film, cleaning with IPA vapor is performed. It was found that when the above was carried out, the surface of the protective film swelled and the interface between the ITO and the protective film was raised, which affected the display quality of the panel. Further, the IPA vapor reduces the adhesion between the color filter and the protective film, and causes a problem that the protective film is peeled off from the substrate in a later process such as a TAB mounting process.

Accordingly, as a coating material excellent in such heat resistance, chemical resistance, etc., JP-A-58-19 / 1983.
Acrylic resins described in JP-A-6506 and JP-A-62-119501, polyglycidyl (meth) acrylate resins described in JP-A-60-216307 and JP-A-4-202418, and JP-A-63-163
No. 131131 discloses a melamine resin, an epoxy resin, a polyimide resin and the like.

[0007]

However, the materials proposed in the prior art have drawbacks, and at present, a balanced material satisfying all the required characteristics has not been obtained.

For example, an acrylic resin has insufficient heat resistance, and has a problem that wrinkles and cracks are generated on the surface of the film during the deposition of ITO or the like.

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

In addition, the polyimide resin has problems such as insufficient transparency, poor storage stability of the varnish, and the ability to use only a solvent that damages the color filter.

Epoxy resins having good adhesiveness have insufficient heat resistance, and those having high heat resistance have poor adhesion and coating properties, so that the required properties cannot be balanced.

On the other hand, polyglycidyl (meth) acrylate resins have good heat resistance and transparency, but have problems in adhesion and alkali resistance under high temperature and high humidity.

Therefore, as described in JP-A-4-202418 and JP-A-4-130128, glycidyl (meth) acrylate has a (meth) acrylate having a hydrophobic alicyclic structure in a side chain; Attempts have been made to improve adhesion by copolymerizing monomers having either N-substituted amides or N-substituted imides.

[0014] However, it has been found that even a coating film formed using the materials specifically disclosed in the above publication has insufficient resistance to IPA vapor.

The present invention solves the above-mentioned drawbacks of the conventional materials, has excellent coating properties and storage stability, and has the heat resistance and chemical resistance required when used as a color filter protective film.
A new resin composition for a cured coating film that satisfies all properties such as adhesion, coating properties, transparency, and scratch resistance, and has significantly improved IPA vapor resistance, a color filter protective film using the same, It is an object to provide a color filter and a liquid crystal display element.

[0016]

Means for Solving the Problems The present invention provides the following (A),
The present invention relates to a cured coating resin composition containing (B) and (C) as essential components. (A): 100 parts by weight of a copolymer containing the following (a1), (a2) and (a3) as monomer components: (a1) N-substituted maleimide (monomer component (a1),
(10 to 45% by weight based on the total amount of (a2) and (a3)) (a2) Glycidyl methacrylate and / or glycidyl acrylate (monomer component (a
1) 55 to 55 based on the total amount of (a2) and (a3)
(A3) optionally used (a1) and (a2)
Unsaturated monomers copolymerizable with (monomer component (a1),
(0 to 30% by weight based on the total amount of (a2) and (a3)) (B): at least one compound 5 to 50 selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids
Parts by weight, and (C): 30 to 100 parts by weight of a functional silane coupling agent

Further, the present invention relates to a resin composition for a cured coating film, which further comprises the following (D) in addition to the above (A), (B) and (C). (D): a copolymer containing the following (d1), (d2) and (d3) as monomer components (d1) N-substituted maleimide (d2) acrylic acid and / or methacrylic acid (d3) optionally used Unsaturated monomer copolymerizable with (d1) and (d2)

The present invention also relates to the monomer component (a)
1) or (d1), wherein the N-substituted maleimide is at least one compound selected from the group consisting of N-alkyl-substituted maleimide, N-cycloalkyl-substituted maleimide, and N-aryl-substituted maleimide. The present invention relates to a resin composition for a film.

The present invention also relates to a color filter protective film using any one of the above resin compositions for a cured coating film.

The present invention also relates to a color filter provided with the color filter protective film.

Further, the present invention relates to a liquid crystal display device having the above-mentioned color filter.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION

I. Resin composition for cured coating film The resin composition for cured coating film of the present invention comprises the following (A) and (B)
And component (C) as an essential component. 1. Essential Component (A) The essential component (A) in the present invention comprises the following (a1), (a)
It is a copolymer containing 2) and (a3) as monomer components. (1) Monomer component (a1) The monomer component (a1) is an N-substituted maleimide.
As the N-substituted maleimide, known ones can be used, and N-alkyl group-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide and N-butylmaleimide; N-cyclohexylmaleimide and the like N-cycloalkyl group-substituted maleimide,
And at least one compound selected from the group consisting of N-aryl group-substituted maleimides such as N-phenylmaleimide and the like, from the viewpoint of heat resistance and adhesion to a substrate. Among these, N-cyclohexylmaleimide and N-phenylmaleimide are more preferred.

(2) Monomer component (a2) The monomer component (a2) is glycidyl methacrylate or glycidyl acrylate. These may be used alone or in combination.

(3) Monomer component (a3) (3) Monomer component (a3) is an unsaturated monomer copolymerizable with (a1) and (a2) used as necessary. Examples of the monomer component (a3) include unsaturated fatty acid esters excluding the monomer component (a2), aromatic vinyl compounds, vinyl cyanide compounds, and the like.

The unsaturated fatty acid ester excluding the monomer component (a2) includes, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate; norbornyl acrylate, nor acrylate Bornylmethyl, adamantyl acrylate, tricycloacrylate [5.2.
1.02,6] decane-8-yl, tricyclo [5.2.2.1.02,6] decane-3 (or 4) -acrylate
Other cycloalkyl acrylates such as ylmethyl, bornyl acrylate, isobornyl acrylate, methylcyclohexyl acrylate, etc. having 7 to 20 carbon atoms in the ring, such as alicyclic acrylates and cyclohexyl acrylates. Aromatic acrylates such as phenyl acrylate and benzyl acrylate, and acrylic esters such as 2-hydroxyethyl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate Esters: norbornyl methacrylate, norbornylmethyl methacrylate, adamantyl methacrylate, tricyclomethacrylate [5.2.1.02,
6] decane-8-yl, tricyclomethacrylate [5.
2.1.02,6] Decane-3 (or 4) -ylmethyl, bornyl methacrylate, isobornyl methacrylate, methylcyclohexyl methacrylate, etc., alicyclic methacrylic having 7 to 20 carbon atoms containing a tertiary carbon in the ring Other than the above, cycloalkyl methacrylates such as acid esters and cyclohexyl methacrylate; aromatic methacrylic esters such as phenyl methacrylate and benzyl methacrylate; and methacrylic esters such as 2-hydroxyethyl methacrylate.

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

As the vinyl cyanide compound, for example,
There are acrylonitrile, methacrylonitrile and the like.

(4) Mixing ratio of monomer components The above-mentioned monomer components (a1), (a2) and (a3)
The mixing ratio of the monomer component (a1) is 10 to 45% by weight, the monomer component (a2) is 55 to 90% by weight, and the monomer component (a3) used as needed is 0 to It is within the range of 30% by weight. If the amount of the (a1) component N-substituted maleimide is less than 10% by weight, the adhesion of the resulting coating film will be insufficient, and if it exceeds 45% by weight, the heat resistance and coating properties will be disadvantageous. If the glycidyl methacrylate and / or glycidyl acrylate component (a2) is less than 55% by weight, the heat resistance of the coating film obtained will be insufficient, and if it exceeds 90% by weight, the adhesion will be reduced. . When the content of the other unsaturated monomer (a3) exceeds 30% by weight, the effect of the present invention becomes insufficient.

In copolymerizing these monomer components (a1), (a2) and (a3), 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, and 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-.
Organic peroxides such as ethylhexanoate and 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexanone; azobisisobutyronitrile, azobis-
Azo compounds such as 4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile and azodibenzoyl; water-soluble catalysts and peroxides represented by potassium persulfate and ammonium persulfate; and persulfuric acid Any one that can be used for ordinary radical polymerization, such as a redox catalyst using a combination of a salt 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 (a1), (a2) and (a3).

As a polymerization regulator, a mercaptan compound, thioglycol, carbon tetrabromide, α-methylstyrene dimer, or the like can be added as needed for controlling the molecular weight. The polymerization temperature is preferably appropriately selected within the range of 0 to 200 ° C, and particularly preferably 50 to 120 ° C.

As a solvent in the solution polymerization, a 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, and ethylene glycol diethyl ether. , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether and other ether solvents; ethyl acetate, n-propyl acetate, 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 Ester-based solvents such as monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol diacetate, and γ-butyrolactone; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Solvents and the like. Of these solvents, ester solvents and ketone solvents are preferred, and they can be used alone or as a mixture of two or more. When used as a resin composition for a cured coating film, since it contains a solvent, it is preferable to polymerize by a solution polymerization method using the same solvent.However, after producing the polymer, the polymer is prepared by a method such as methanol reprecipitation method. Can be isolated and used after being dissolved in another solvent.

The molecular weight of the essential component (A) is not particularly limited as long as the composition of the present invention can be applied to a substrate as a uniform film, but is usually 5,000 to 300,000.
(Weight average molecular weight in terms of polystyrene) and can be appropriately selected depending on the purpose and conditions of the film formation, such as the thickness of the cured coating film to be formed and the application method.

2. Essential Component (B) In the present invention, at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids is used as the essential component (B).

Examples of the polycarboxylic anhydride include itaconic anhydride, maleic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Methyl hexahydrophthalic anhydride,
Aliphatic dicarboxylic anhydrides such as endmethylenetetrahydrophthalic anhydride and methylendmethylenetetrahydrophthalic anhydride; Fats such as cyclopentanetetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Aromatic polycarboxylic dianhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, 3,3 ', 4,4'-
Aromatic polycarboxylic anhydrides such as diphenylsulfonetetracarboxylic dianhydride; ester group-containing anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate; 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 And aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid and benzophenonetetracarboxylic acid.

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

In the composition of the present invention, the essential component (B)
Is 5 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the copolymer of the essential component (A). If the compounding ratio is less than 5 parts by weight, the heat resistance becomes insufficient, and if it exceeds 50 parts by weight, the applicability, chemical resistance and the like are reduced.

3. Indispensable Component (C) In the present invention, a functional silane coupling agent is used as the C component in order to improve adhesion and IPA vapor resistance. As the functional silane coupling agent, a silane coupling agent having a reactive substituent such as a vinyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, and an epoxy group, specifically, vinyltrimethoxysilane, Vinyl triethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like can be mentioned. Particularly, a silane coupling agent having an epoxy group is preferable because of excellent adhesion, chemical resistance and the like. These functional silane coupling agents may be used alone or in combination of two or more.

The mixing ratio of the essential component (C) is from 30 to 100 based on 100 parts by weight of the copolymer of the essential component (A).
Parts by weight, preferably 30 to 60 parts by weight. If the compounding ratio is less than 30 parts by weight, adhesion and IPA vapor resistance become insufficient, and if it exceeds 100 parts by weight, coating properties and heat resistance deteriorate.

4. Component (D) In the present invention, if necessary, the following (d1), (d)
It is preferable to use component (D) which is a copolymer containing (2) and (d3) as monomer components from the viewpoint of improving the adhesion to the substrate after IPA vapor treatment. (D1) N-substituted maleimide (d2) Acrylic acid and / or methacrylic acid (d3) optionally used unsaturated monomer copolymerizable with (d1) and (d2)

As the N-substituted maleimide which is the monomer component (d1), those which are exactly the same as the N-substituted maleimide of the above (a1) can be used, and N-cyclohexylmaleimide and N-phenylmaleimide are heat-resistant and have a base material. It is particularly preferable from the viewpoint of the adhesion to the substrate.

Acrylic acid or methacrylic acid as the monomer component (d2) may be used in combination.

The unsaturated monomer monomer component (d3) copolymerizable with the monomer component (d1) or (d2) includes unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds and the like. Specific examples thereof include the monomers exemplified as the monomer component (a3) of the copolymer of the essential component (A).

The proportions of the above-mentioned monomer components (d1), (d2) and (d3) are, based on the total amount thereof, 20 to 70% by weight of the monomer component (d1) and 5 to 5% by weight of the monomer component (d2). It is preferred to use 30% by weight and 0 to 50% by weight of the monomer component (d3). When the mixing ratio of the monomer component (d1) is 20
If the amount is less than 10% by weight, the heat resistance of the obtained coating film tends to be insufficient, and if it exceeds 70% by weight, the adhesion and the coating property tend to be disadvantageous. If the amount of the monomer component (d2) is less than 5% by weight, the heat resistance and scratch resistance of the resulting coating film tend to be insufficient. If it exceeds 30% by weight, the coating property and the chemical resistance of the coating film tend to be insufficient. Properties tend to decrease. If the amount of the monomer component (d3) exceeds 50% by weight, the effect of the present invention tends to be insufficient.

The copolymer as component (D) is composed of these monomer components (d1) and (d2) and, if necessary, (d)
It can be produced by blending 3) and copolymerizing. In this case, the polymerization method, the polymerization initiator that can be used, the polymerization temperature, the solvent in the solution polymerization,
This is the same as in the case of the copolymer which is the essential component (A).

The mixing ratio of the component (D) in the composition is as follows:
0 parts by weight based on 100 parts by weight of the copolymer as the essential component (A)
It is preferable to use it in the range of 100 parts by weight. If the compounding ratio of the component (D) exceeds 100 parts by weight, heat resistance, chemical resistance, and the like tend to decrease.

5. Formation of Coating Film The composition of the present invention can be usually dissolved in a solvent, applied to a substrate, 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 the solvent when the copolymer as the essential component (A) or the component (D) of the present invention is subjected to solution polymerization are exemplified. Of these solvents, ester solvents and ketone solvents are preferred, and they can be used alone or as a mixture of two or more.

The method for preparing the 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 simultaneously dissolving all the components in the solvent. Depending on each component as appropriate two or more solutions,
At the time of use, these solutions may be mixed to form a composition solution. The amount of the solvent used when preparing the composition solution in this manner is preferably 50 to 95% by weight based on the total amount of the final composition solution to be applied. If the content is less than 50% by weight, the solid content concentration is too high, and the leveling property of the coating film may be reduced, or the transparency of the coating film may be reduced. If it exceeds 95% by weight, the solid content concentration is too low. As a result, the chemical resistance of the coating film may be insufficient. The composition of the present invention may further contain, if necessary, an epoxy resin such as an epibis type or a novolak type, a curing accelerator, a stabilizer such as an antioxidant or an ultraviolet absorber, and the like.

6. Coating method There is no particular limitation on the application of the composition solution of the present invention. In addition to a dipping method, a spray method, a roll coating method, a spin coating method and the like, a substrate is applied by a coating method such as screen printing and offset printing. Can be applied. The heat-curing conditions of the composition of the present invention are appropriately selected depending on the specific types, blending ratios, and the like of each component of the composition.
0.1 ~ 10 hours at ~ 300 ° C, preferably 100 ~ 2
It is about 1 to 5 hours at 50 ° C.

II. Color filter protective film The cured coating film formed by the composition of the present invention shows excellent adhesion to various materials such as glass, metal, and plastic, and is smooth, tough, light-resistant, heat-resistant, and water-resistant. Since it has excellent solvent resistance and transparency, it is useful as a coating film for various articles. In particular, as a color filter protective film, as a surface protective layer and a flattening layer of various color filters obtained by dyeing various binder resins such as gelatin, glue, polyvinyl alcohol, and acrylic resin with a dye or dispersing a pigment. Useful.
When used as a color filter protective film, the film thickness after heat curing is 0.005 to 30 μm, preferably 0.1 to 10 μm.
It can be appropriately coated and used so as to have a thickness of about μm.

The conventional coating materials have drawbacks in the properties of the color filter protective film, and all the properties required for the color filter protective film, such as coating properties, heat resistance, and chemical resistance, are not satisfied. Although there was nothing to satisfy, the composition of the present invention can satisfy these required properties in a well-balanced manner by combining a compound having a specific structure. Using the color filter protective film of the present invention, a color filter can be obtained by a conventional method,
Further, a liquid crystal display element can be obtained using the color filter.

[0052]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. [Production Example 1] Synthesis of copolymer solution (A-1) Ethyl cellosolve acetate (ethylene glycol) was used as a polymerization solvent in a 1-liter flask equipped with a stirrer, thermometer, nitrogen inlet tube, reflux condenser, and dropping funnel. 260 parts by weight of monoethyl ether acetate) were charged, and the atmosphere in the flask was replaced with nitrogen. 80 parts by weight of N-phenylmaleimide as a monomer, glycidyl methacrylate 1
20 parts by weight of azobisisobutyronitrile as a polymerization initiator and 1.0 part by weight of butyl cellosolve acetate 100
The resulting solution was added dropwise to the above-mentioned 1-liter flask at 90 ° C. for 3 hours in a nitrogen stream. At 90 ° C
After stirring for an hour, a solution prepared by dissolving 0.2 parts by weight of azobisisobutyronitrile in 40 parts by weight of butyl cellosolve acetate was added, and then the temperature was raised to 120 ° C. and maintained for 2 hours.

The obtained copolymer was analyzed by HLC (GPC mode; column: Gelpack A- manufactured by Hitachi Chemical Co., Ltd.).
120+ gel pack A-140 + gel pack A-15
0, eluent: tetrahydrofuran, detector: differential refractometer), the polystyrene equivalent weight average molecular weight was about 45,000.

[Production Example 2] Copolymer resin solution (A-
Synthesis of 2) In Production Example 1, the monomers were N-cyclohexylmaleimide (60 parts by weight), glycidyl methacrylate (120 parts by weight), and tricyclomethacrylate [5.2.1.02,6].
Dec-3-en-8 or 9-yl-oxyethyl 20
Except that it was changed to parts by weight, it was carried out in exactly the same way as in Production Example 1,
HLC analysis of the obtained copolymer revealed that the weight average molecular weight in terms of polystyrene was about 55,000.

Production Example 3 Synthesis of Copolymer Solution (A-3) In Production Example 1, the monomer was N-phenylmaleimide 6
The same procedure as in Production Example 1 was carried out except that the amount was changed to 0 parts by weight and 140 parts by weight of glycidyl methacrylate, and the obtained copolymer was subjected to HLC analysis. As a result, the weight average molecular weight in terms of polystyrene was about 42,000. .

[Production Example 4] Synthesis of Copolymer Solution (A-4) In Production Example 1, the monomers were 40 parts by weight of N-cyclohexylmaleimide, 140 parts by weight of glycidyl methacrylate, and tricyclo [5.2 methacrylate]. 1.02, 6]
Dec-3-en-8 or 9-yl-oxyethyl 20
Except that it was changed to parts by weight, it was carried out in exactly the same way as in Production Example 1,
HLC analysis of the obtained copolymer revealed that the weight average molecular weight in terms of polystyrene was about 45,000.

[Reference Production Example 1] Copolymer solution (D-
Synthesis of 1) 150 parts by weight of ethyl cellosolve acetate as a polymerization solvent 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 flask was purged with nitrogen. 100 parts by weight of N-phenylmaleimide, 40 parts by weight of methacrylic acid, 60 parts by weight of ethyl acrylate, and 3.0 parts by weight of azobisisobutyronitrile as monomers are ethyl cellosolve acetate 3
The resulting solution was added dropwise to the above 1 liter flask at 90 ° C. for 3 hours in a nitrogen stream. 90 ° C
After stirring for 1 hour with azobisisobutyronitrile 0.1.
A solution obtained by dissolving 2 parts by weight of ethyl cellosolve acetate in 16.7 parts by weight was added, and then the temperature was raised to 120 ° C.
Time kept.

When the obtained copolymer was analyzed by HLC, the weight average molecular weight in terms of polystyrene was about 15,000.
It was 0.

[Reference Production Example 2] Copolymer solution (A-
Synthesis of 5) In Production Example 1, the monomer was glycidyl methacrylate 1
40 parts by weight, tricyclomethacrylate [5.2.1.0
The same procedure as in Production Example 1 was carried out except that the amount was changed to 60 parts by weight of 2,6] decane-8-yl.
C analysis revealed that the weight average molecular weight in terms of polystyrene was about 42,000.

[Reference Production Example 3] Copolymer solution (A-
Synthesis of 6) In Production Example 1, the monomer was N-phenylmaleimide 1
The same procedure as in Production Example 1 was carried out except that the amount was changed to 00 parts by weight and glycidyl methacrylate was changed to 100 parts by weight, and the obtained copolymer resin was subjected to HLC analysis. As a result, the weight average molecular weight in terms of polystyrene was about 56,000. .

[Examples 1 to 6] Ethyl cellosolve acetate was added to the copolymer solution and other components according to the formulations shown in Table 1 (the unit of the formulation is parts by weight), and the mixture was uniformly mixed and dissolved at room temperature. , An initial viscosity of 15 to 20 centipoise (2
(5 ° C.).

After the solution was filtered through a membrane filter having a pore size of 0.2 μm, the solution was spin-coated at 700 rpm on a glass plate (7059 material, Dow Corning Co., Ltd., non-alkali glass) using a spin coater. After application,
The glass plate was treated in a clean oven at 200 ° C. for 1 hour to cure the coating. The surface of the obtained coating film was extremely smooth, and no pinholes or the like were observed. Stylus type film thickness meter (manufactured by Nihon Vacuum Engineering Co., Ltd .; trade name: Dektak3)
The film thickness measured by ST) was 1.5 to 2.5 μm.

The following tests were carried out on the coating films thus produced. Goban eye test (JIS-K-54) by tape peeling to examine the adhesion of the coating film to the glass plate
00). As a result, the remaining number was 100/100, and no peeling was observed. Next, 400nm of coating film
The light transmittance was 95% or more in the whole region when the same glass plate as that on which the absorption spectrum at -800 nm was applied was measured as a reference.

The glass plate with the coating film was subjected to a pressure cooker test (120 ° C., 2 atm, 10 hours).
(Hereinafter referred to as PCT treatment), immersed in N-methylpyrrolidone at room temperature for 1 hour (hereinafter referred to as NMP treatment), and immersed in a 5% by weight aqueous sodium hydroxide solution at room temperature for 1 hour (hereinafter referred to as NaOH treatment). A treatment of immersion in a 1% by weight aqueous solution of hydrochloric acid at room temperature for 1 hour (hereinafter referred to as HCl treatment) was performed separately, and after each treatment, the above-mentioned goban test and measurement of light transmittance were performed. When these results were compared with the test results immediately after the coating film was cured, the adhesiveness and light transmittance were good in each case. Table 2 shows the results of the Goban test.
And Table 3 show the results of the light transmittance test.

[Comparative Examples 1 to 4] Ethyl cellosolve acetate was added to the copolymer solution and other components in the composition shown in Table 1 in the same manner as in Examples 1 to 6, and the mixture was uniformly mixed at room temperature.
Dissolve and have an initial viscosity of 15-20 centipoise (25
C). The obtained solution was applied on a glass plate and cured by heating in the same manner as in the examples, and various property tests were performed on coating films having a film thickness of 1.5 to 2.5 μm. Table 2 shows the results of the Goban order test, and Table 3 shows the results of the light transmittance test.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[Example 7] The composition solutions prepared in Examples 1 to 6 were applied on a color filter substrate produced by a generally known method, and then cured by heating to form a protective film. The characteristics of the color filter with a protective film were examined.

A color filter substrate is prepared by using a gelatin and potassium dichromate solution on a transparent glass substrate and using a dye-type color filter of three colors of red, green and blue in a stripe shape by a conventional method. (Stripe width 100μ)
m). The pixel film thickness of this substrate was measured by a stylus type film thickness meter (manufactured by Nippon Vacuum Engineering Co., Ltd .; trade name: Dektak3ST), and it was 1.0 μm.

Next, the composition solution was spin-coated at 700 rpm on the color filter substrate, and cured by heating at 180 ° C. for 1 hour to form a protective film. An indium tin oxide (ITO) film is formed on the thus-prepared color filter with a protective film by sputtering at a substrate temperature of 150.degree. C. so as to have a thickness of 3,000.degree. It was left for 30 minutes. When this substrate was observed in detail with an optical microscope, no wrinkles or cracks were observed on the color filter or the protective film.

Further, the ITO film was patterned by photolithography, and a Gobang test was performed after the PCT treatment. The adhesion between the color filter and the protective film, and the adhesion between the ITO and the protective film were good as shown in Table 4. .

Further, the color filter having the ITO pattern was allowed to stand in a vapor tank of isopropyl alcohol (IPA) for 30 minutes and then observed in detail with an optical microscope. No abnormality was found on the ITO surface and the protective film surface. .

Comparative Example 5 The suitability for a color filter substrate was examined in exactly the same manner as in Example 7, except that the composition solutions prepared in Comparative Examples 1 to 4 were used. The results are shown in Table 4.

[0075]

[Table 4]

[0076]

The resin composition for a cured coating film of the present invention has excellent coatability and storage stability, and a coating film formed using this resin composition has smoothness, transparency, and close (contact) adhesion. It is extremely excellent in water resistance, moisture resistance, chemical resistance, heat resistance, scratch resistance, IPA vapor resistance and the like. In addition, the color filter protective film of the present invention is formed using the resin composition for a cured coating film, and has excellent characteristics similar to those of a coating film formed from the resin composition. And a liquid crystal display device having the same.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G02F 1/1335 505 G02F 1/1335 505

Claims (6)

[Claims] 1. A resin composition for a cured coating film comprising the following (A), (B) and (C) as essential components. (A): 100 parts by weight of a copolymer containing the following (a1), (a2) and (a3) as monomer components: (a1) N-substituted maleimide (monomer component (a1),
(10 to 45% by weight based on the total amount of (a2) and (a3)) (a2) Glycidyl methacrylate and / or glycidyl acrylate (monomer component (a
1) 55 to 55 based on the total amount of (a2) and (a3)
(A3) optionally used (a1) and (a2)
Unsaturated monomers copolymerizable with (monomer component (a1),
(0 to 30% by weight based on the total amount of (a2) and (a3)) (B): at least one compound 5 to 50 selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids
Parts by weight, and (C): 30 to 100 parts by weight of a functional silane coupling agent 2. In addition to (A), (B) and (C),
The resin composition for a cured coating film according to claim 1, further comprising the following (D). (D): a copolymer containing the following (d1), (d2) and (d3) as monomer components (d1) N-substituted maleimide (d2) acrylic acid and / or methacrylic acid (d3) optionally used Unsaturated monomer copolymerizable with (d1) and (d2) 3. The N of the monomer component (a1) or (d1)
-A substituted maleimide is an N-alkyl group-substituted maleimide,
The resin composition for a cured coating film according to claim 1 or 2, wherein the resin composition is at least one compound selected from the group consisting of an N-cycloalkyl group-substituted maleimide and an N-aryl group-substituted maleimide. 4. A color filter protective film using the resin composition for a cured coating film according to claim 1. 5. A color filter comprising the color filter protective film according to claim 4. 6. A liquid crystal display device comprising the color filter according to claim 5.