JP2001158816A - Curable composition and film for protecting color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable composition capable of providing a cured product excellent in heat resistance, flatness and transparency, especially a film for protecting a color filter, excellent in the heat resistance and the transparency. SOLUTION: This curable composition comprises [A] a copolymer of (a1) a monomer containing an epoxy group, (a2) a maleimide-based monomer and (a3) other monomers, [B] at least one compound selected from a group of a polybasic carboxylic acid anhydride and a polybasic carboxylic acid, and [C] an epoxy resin different from the component [A]. The film for protecting the color filter is formed therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition and a color filter protective film. More specifically, the present invention relates to a curable composition and a color filter protective film which can provide a cured product having excellent heat resistance and transparency and are therefore suitable for forming a color filter protective film.

[0002]

2. Description of the Related Art Super twisted nematic (ST)
The N) type color liquid crystal display element is manufactured through a process of forming a transparent electrode film on a color filter protective film and further forming a liquid crystal alignment film thereon. At that time, since heating is performed in the step of forming the transparent electrode film and the step of forming the liquid crystal alignment film, the temperature of the protective film rises to 250 ° C. or higher, and when the heat resistance of the protective film is not sufficient, the transparent electrode film Evaporation from the protective film may invade and increase the resistance of the transparent electrode film to reduce conduction, or the protective film itself may be colored to reduce transparency.

Conventionally, as a material for a protective film, Japanese Patent Laid-Open No.
A copolymer described in 157716 has been known, but such a copolymer had a problem to be solved as described above.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition which gives a cured product having excellent heat resistance, flatness and transparency. Another object of the present invention is to
An object of the present invention is to provide a color filter protective film formed from the curable composition of the present invention and having excellent heat resistance and transparency. Yet another object of the present invention is to provide use of the curable composition of the present invention for forming a color filter protective film. Still other objects and advantages of the present invention will become apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention are as follows: [A] (a1) an epoxy group-containing monomer, (a2) a maleimide monomer and (a3) other And [B] at least one compound selected from the group consisting of polycarboxylic anhydrides and polycarboxylic acids, and [C] an epoxy resin different from the component [A]. This is achieved by a curable composition characterized in that: The curable composition of the present invention may optionally further contain [D] an acid generator.

The above objects and advantages of the present invention are, second,
This is achieved by using the curable composition of the present invention for forming a color filter protective film. Third, still other objects and advantages of the present invention are achieved by a color filter protective film formed from the curable composition of the present invention.

Hereinafter, each component of the curable composition of the present invention will be described in detail. Copolymer [A] The copolymer [A] can be produced by subjecting compound (a1), compound (a2) and compound (a3) to radical polymerization in a solvent in the presence of a polymerization initiator. .

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a1), preferably 1
The content is 0 to 70% by weight, particularly preferably 20 to 60% by weight. A copolymer containing less than 10% by weight of the structural unit tends to lower the heat resistance and surface hardness of the resulting protective film. On the other hand, if it exceeds 70% by weight, the storage stability of the curable composition tends to decrease. As the epoxy group-containing monomer (a1), the following formula (1)

[0009]

Embedded image Wherein R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² is a hydrogen atom, a methyl group or an ethyl group, and m is a number of 1 to 8. Can be mentioned.

In the above formula (1), m is an integer of 1 to 8, preferably 1 to 4. R ¹ is a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms. The lower alkyl group may be any of a linear group and a branched group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Butyl group, isobutyl group, sec-butyl group, tert
-Butyl and n-pentyl. Further, R ² is a hydrogen atom, a methyl group or an ethyl group.

Examples of the monomer represented by the above formula (1) include glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and ( 3,4-epoxybutyl (meth) acrylate, 4,5-epoxypentyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, 6,7-epoxyheptyl α-ethylacrylate And methyl glycidyl (meth) acrylate. Of these, glycidyl (meth) acrylate is particularly preferred. These monomers can be used alone or in combination of two or more.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a2), preferably 2
-50% by weight, particularly preferably 5-40% by weight. If this constituent unit is less than 5% by weight, heat resistance, chemical resistance, and surface hardness tend to decrease. This structural unit is 5
If it exceeds 0% by weight, the film-forming property of the coating film tends to decrease.

As the maleimide-based monomer (a2),
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-
3-maleimidobenzoate, N-succinimidyl-
4-maleimidobutyrate, N-succinimidyl-6
Maleimide caproate, N-succinimidyl-3
-Maleimide propionate and N- (9-acridinyl) maleimide. These can be used alone or in combination of two or more.

The copolymer [A] used in the present invention contains the structural unit derived from the other monomer (a3) in an amount of preferably 5 to 80% by weight, particularly preferably 10 to 70% by weight.
% By weight. If this constituent unit is less than 5% by weight, the film formability of the coating film may be insufficient, and if this constituent unit exceeds 80% by weight, heat resistance and chemical resistance may be insufficient.

Examples of the other monomer component (a3) include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; and acrylics such as methyl acrylate and isopropyl acrylate. Acid alkyl esters; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate (commonly referred to in the art as dicyclopentanyl methacrylate) Methacrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl methacrylate and isobornyl methacrylate; cyclohexyl acrylate, 2
-Methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (commonly referred to in the art as dicyclopentanyl acrylate), dicyclopentanyloxyethyl acrylate Acrylic acid cyclic alkyl esters such as isobornyl acrylate; methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; diethyl maleate, diethyl fumarate and diethyl itaconate Dicarboxylic acid diesters; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and styrene, α
-Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-
Methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and the like are preferred from the viewpoint of copolymerization reactivity. These may be used alone or in combination.

Examples of the solvent used for producing the copolymer [A] include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Glycol ethers; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether; Propylene glycol ethyl ether, professional Glycol propyl ether,
Propylene glycol monoalkyl ethers such as propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; propylene glycol methyl ether propionate Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, Ketones such as roxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methyl propionate,
Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate,
Ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate , Ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate,
Methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-
Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxy Ethyl propionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxypropion Methyl acrylate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxyp Acid propyl, 3-propoxy-propionic acid butyl, 3-butoxy-propionic acid methyl 3- butoxy-propionic acid ethyl, 3-butoxy-propionic acid propyl, 3-butoxy esters such as acid butyl.

As the polymerization initiator used for producing the copolymer [A], those generally known as a radical polymerization initiator can be used. For example, 2,2′-azobisisobutyronitrile, Azo compounds such as 2,2'-azobis- (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t- Organic peroxides such as butylperoxypivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

The copolymer [A] used in the present invention has a polystyrene equivalent weight average molecular weight (hereinafter, referred to as “Mw”) of usually 2 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 × 10 ⁵ .
Desirably, it is 10 ³ to 1 × 10 ⁵ . Mw is 2 × 1
If it is less than 0 ^3, the resulting coating tends to heat resistance, surface hardness decreases. On the other hand, when it exceeds 5 × 10 ⁵ , the flatness tends to decrease.

Component [B] The polycarboxylic acid anhydride or polycarboxylic acid used as the component [B] functions as a curing agent for the specific polymer used as the component [A].

Specific examples of polycarboxylic anhydrides include:
Aliphatic dicarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride; Alicyclic polycarboxylic dianhydrides such as 2,3,4-butanetetracarboxylic dianhydride and cyclopentanetetracarboxylic dianhydride; phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and anhydride Aromatic polycarboxylic acid anhydrides such as benzophenonetetracarboxylic acid; and ester group-containing acid anhydrides such as ethylene glycol bis trimellitate anhydride and glycerin tris trimellitate anhydride. Among them, the use of aromatic polycarboxylic anhydrides, particularly trimellitic anhydride, is preferred in that a cured film having high heat resistance can be obtained.

Further, specific examples of the polyvalent carboxylic acid include:
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid And alicyclic polycarboxylic acids such as cyclopentanetetracarboxylic acid; aromatic polyvalent acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and 1,2,5,8-naphthalenetetracarboxylic acid. And carboxylic acids. Among these, aromatic polycarboxylic acids are preferred from the viewpoint of the reactivity of the curable composition, the heat resistance of the formed cured film, and the like. These polycarboxylic anhydrides and polycarboxylic acids can be used alone or in combination of two or more.

The proportion of the component [B] is usually preferably 1 to 100 parts by weight, more preferably 10 to 70 parts by weight, per 100 parts by weight of the component [A]. When the proportion of the component (B) is less than 1 part by weight, it is difficult to obtain a cured film having a sufficiently high crosslink density, and the various resistances of the cured film may be reduced. On the other hand, when the proportion of the component [B] exceeds 100 parts by weight, a large amount of the unreacted component [B] tends to remain in the obtained cured film, and as a result, the properties of the cured film are unstable. Or the adhesion of the cured film to the substrate may be reduced.

[C] Component As the epoxy resin different from the component [A], for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin and the like can be used. These are commercially available. For example, bisphenol A type epoxy resins include Epicoat 1001,
002, 1003, 1004, 1007, 10
Nos. 09, 1010, and 828 (both manufactured by Yuka Shell Epoxy Co., Ltd.) and the like, and as bisphenol F type epoxy resins, Epicoat 807 and 834 (both manufactured by Yuka Shell Epoxy Co., Ltd.) and the like, Examples of the phenol novolak type epoxy resin include Epicoat 152, 154, and 157H65 (all manufactured by Yuka Shell Epoxy Co., Ltd.),
EPPN201, EPPN201 (all made by Nippon Kayaku Co., Ltd.)
Etc., as cresol novolak type epoxy resin,
EOCN-102, EOCN-103S, EOCN-1
04S, EOCN-1020, EOCN-1025, E
OCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), etc., and CY17 as a cycloaliphatic epoxy resin
5, CY177, CY179 (above, CIBA-GEI
GY A. G), ERL-4234, ERL-429
9, ERL-4221, ERL-4206 (the above.
C. C), Shodyne 509 (Showa Denko KK)
CY-182, CY-192, and CY-184 (manufactured by CIBA-GEIGY AG)
Epicron 200, Epicron 871, Epilon 872, EP (above, manufactured by Dainippon Ink Industries, Ltd.)
1032H60 (above, Yuka Shell Epoxy Co., Ltd.)
ED-5661, ED-5662 (all made by Celanese Coatings Co., Ltd.) and the like as epipoly 190P and 191P as aliphatic polyglycidyl ethers.
(The above is made by Yuka Shell Epoxy Co., Ltd.) Epolite 10
0MF (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Epiol T
MP (manufactured by NOF Corporation) and the like.

Among these, preferred are bisphenol A type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin. The usage ratio of the epoxy resin [C] is preferably 1 to 200 parts by weight, more preferably 3 to 100 parts by weight, per 100 parts by weight of the component [A]. The component [A] is also an epoxy resin, but the epoxy resin of the component [C] is different from the component [A] in that it has a low molecular weight and is effective in improving flatness. The curable composition of the present invention can further contain an acid generator [D], if necessary.

[D] Component As the compound that generates an acid by heat, onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts are used. Among them, sulfonium salts and benzothiazonium salts are preferred.

Specific examples of the above sulfonium salt include 4
-Acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-
4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-
Alkylsulfonium salts such as 4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate; benzyl -4-Hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl -2-methyl-4-hydroxyphenylmethylsulfonium hexafluoro Nchimoneto, benzyl-3-chloro-4-hydroxyphenyl methyl sulfonium hexafluoroarsenate, benzyl sulfonium salts, such as 4-methoxybenzyl-4-hydroxyphenyl methyl sulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-
tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-
Dibenzylsulfonium salts such as 4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chloro Benzyl-4
-Hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-
4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4
Substituted benzylsulfonium salts such as -hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; sulfonium salts represented by the following formulas (1) to (7) Is mentioned.

[0029]

Embedded image

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3-benzylbenzothiazonium tetrafluoroborate. (P-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5
Benzylbenzothiazonium salts such as -chlorobenzothiazonium hexafluoroantimonate.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium
Hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate Nates and the like are preferably used. These commercial products include Sun-Aid SI-L85,
I-L110, SI-L145, SI-L150,
And SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.). These compounds that generate an acid by heat can also function as compounds that generate an acid by radiation. These compounds can be used alone or in combination of two or more.

The compound [D] which generates an acid by heat is preferably used in an amount of 0.01 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the component [A]. It is. When the proportion of the component [D] used is 100 for the component [A].
When the amount is less than 0.01 part by weight, the amount of the acid generated by heating is small, so that the cross-linking of the component [A] and the component [C] hardly proceeds sufficiently, and the resulting cured film has Heat resistance, flatness, chemical resistance, adhesion to a substrate, and the like may decrease. On the other hand, the usage ratio of the component [D] [A]
If the amount exceeds 20 parts by weight with respect to 100 parts by weight of the component, the coating film tends to be rough.

<Other Components> In addition to the above-mentioned components [A], [B], [C] and [D], the curable composition of the present invention may further contain other components as necessary. As
For example, a silane coupling agent, a curing accelerator, a surfactant, an ultraviolet absorber, and the like may be contained.

[Silane Coupling Agent] The silane coupling agent is used for improving the adhesion between the cured film and the substrate on which the cured film is to be formed, and includes a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. A functional group-containing alkoxysilane compound having a reactive substituent (functional group) such as a group is used.

Examples of such functional group-containing alkoxysilane compounds include trimethoxysilylbenzoic acid,
γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyldiethoxysilane and the like. These can be used alone or in combination of two or more.

The proportion of the silane coupling agent used is preferably 100 parts by weight or less, more preferably 0.1 to 100 parts by weight, particularly preferably 1 to 40 parts by weight with respect to 100 parts by weight of the component [A]. is there. If the use ratio of the silane coupling agent is less than 0.1, the effect of providing sufficient adhesion between the cured film and the substrate on which the cured film is to be formed may not be obtained. On the other hand, if the use ratio of the silane coupling agent exceeds 100 parts by weight, the resulting cured film may have reduced alkali resistance, solvent resistance and the like.

[Curing accelerator] The curing accelerator is used for accelerating the reaction with the component [A] and the component [B], that is, the curing agent, and is generally a secondary nitrogen atom or a tertiary nitrogen atom. A compound having a heterocyclic structure containing is used. Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine,
Examples include pyrimidine, indole, indazole, benzimidazole, isocyanuric acid, and derivatives thereof. Among these, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2
-Heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1 −
[2 ′-(3 ″, 5 ″ -diaminotriazinyl) ethyl] imidazole derivatives such as imidazole and benzimidazole are preferred, and most preferably 2-ethyl-4.
-Methylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole and the like are used. These compounds can be used alone or in combination of two or more as a curing accelerator.
The curing accelerator is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the component [A].
Used in a proportion of 5 parts by weight.

[Surfactant] As the surfactant, a fluorine-based surfactant and a silicone-based surfactant can be suitably used. As the fluorinated surfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of terminal, main chain and side chain can be suitably used.
1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2 -Tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-
Hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,
3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,
9,9,10,10-decafluorododecane, 1,1,2,2,
3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyloxyethylene ether, diglycerin tetrakis, fluoroalkylammonium iodide, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol, perfluoroalkylalkoxylate,
Fluorinated alkyl esters and the like can be mentioned. Further, as these commercially available products, BM-1000, BM-
1100 (all manufactured by BM Chemie), MegaFac F142D, F172, F173, F18
3, F178, F191, F471 (all manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-170
C, FC-171, FC-430, and FC-431 (all manufactured by Sumitomo 3M Limited) and the like.

Examples of the silicone surfactant include Toray silicone DC3PA, DC7PA, S
H11PA, SH21PA, SH28PA, SH
29PA, SH30PA, FS-1265-300
(The above are manufactured by Toray Silicone Co., Ltd.), TSF-444
0, TSF-4300, TSF-4445, TSF-4
446, TSF-4460, TSF-4452 (or more,
And those marketed under the trade name of Toshiba Silicone Co., Ltd.).

These surfactants can be used alone or in combination of two or more. The use ratio of the surfactant varies depending on the type thereof, the type and ratio of each component constituting the curable composition, and preferably, 0 to 10 parts by weight, more preferably 100 parts by weight of component [A]. Preferably it is used in the range of 0.0001 to 5 parts by weight.

Preparation of Curable Composition The curable composition of the present invention is advantageously used in the form of a solution after being dissolved in a suitable solvent. For example, copolymer [A],
By mixing the component [B], the component [C], the optionally added component [D], and other compounding agents at a predetermined ratio, a curable composition in a solution state can be prepared.

As the solvent used for preparing the curable composition of the present invention, a solvent which uniformly dissolves the copolymer [A] and does not react therewith is used. Specifically, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetate such as methyl cellosolve acetate and ethyl cellosolve acetate Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol Propylene glycol alkyl ether acetates such as tyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether pro Propylene glycol alkyl ether acetates such as pionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid methyl,
Ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate,
Butyl lactate, methyl 3-hydroxypropionate, 3-
Ethyl hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate,
Esters such as ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate are exemplified.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycols are preferably used from the viewpoint of solubility, reactivity with each component, and ease of forming a coating film. .

Further, a high boiling point solvent can be used in combination with the above-mentioned solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.
The composition solution prepared as described above has a pore size of 0.5.
After filtration using a millimeter filter of about μm,
It can also be used for use.

The concentration of the curable composition in the composition solution is not particularly limited and can be appropriately selected according to the purpose of use. The concentration of the solid content is preferably 1 to 60% by weight, more preferably 5 to 40% by weight.

Method for Forming Color Filter Protective Film By using the curable composition of the present invention, a cured film can be formed, for example, as follows. That is,
By applying the prepared composition solution to the surface of the substrate on which a cured film is to be formed, removing the solvent by performing preliminary firing, forming a coating film of the curable composition, and then performing main firing. And a cured film.

In the above, the method of applying the composition solution is not particularly limited, and various methods such as a spray method, a roll coating method and a spin coating method can be employed. The conditions for the pre-baking vary depending on the type of each component of the composition solution, the usage ratio, and the like, but preferably are 60 to 12 times.
At 0 ° C. for about 0.5 to 20 minutes. The conditions for the main firing are preferably at about 150 to 250 ° C. for about 0.2 to 2.0 hours. In addition, each of the preliminary firing and the main firing can be performed in one step or in a combination of two or more steps.

[0048]

EXAMPLES The present invention will be described more specifically with reference to the following synthesis examples and examples, but the present invention is not limited to the following examples.

Synthesis Example 1 A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 20 parts by weight of styrene, 65 parts by weight of glycidyl methacrylate, and 15 parts by weight of N-phenylmaleimide were charged and replaced with nitrogen, and then gentle stirring was started. The temperature of the solution was raised to 95 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1].
The solid content concentration of the obtained polymer solution was 32.8%.

Synthesis Example 2 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, 18 parts by weight of styrene, 62 parts by weight of glycidyl methacrylate, and 20 parts by weight of N-cyclohexylmaleimide were charged and replaced with nitrogen, and then gentle stirring was started. The temperature of the solution was raised to 95 ° C. and this
After holding for a time, a polymer solution containing the copolymer [A-2] was obtained. The solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 3 A flask equipped with a condenser and a stirrer was charged with 6,2 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, dicyclopentanyl methacrylate 40
After weight parts and 60 parts by weight of glycidyl methacrylate were charged and purged with nitrogen, gentle stirring was started. The temperature of the solution was raised to 95 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 32.8%.

Synthesis Example 4 6 parts by weight of 2,2′-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, 20 parts by weight of styrene and 80 parts by weight of glycidyl methacrylate were charged and replaced with nitrogen, and then gentle stirring was started. The temperature of the solution was raised to 95 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-4]. The solid concentration of the obtained polymer solution is 32.4.
%Met.

Example 1 A polymer solution containing the polymer [A-1] synthesized in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the polymer [A-1]) was treated with propylene glycol monomethyl ether acetate 100 20 parts by weight of Epicoat 1032H60 (cycloaliphatic epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) as a component [C], and γ-glycidoxypropyldiethoxysilane as a silane coupling agent 5 parts by weight and Megafac 17 as a surfactant
2 (Fluorine surfactant, Dainippon Ink and Chemicals, Inc.)
20% by weight of a 25% solution of trimellitic anhydride in diethylene glycol methyl ethyl ether as a curing agent for component [B] as a hardener of component [B] was added, and the mixture was sufficiently stirred. Curable composition (S
-1) was obtained.

On the glass substrate on which the protective film (I) is formed , the above curable composition [S1] is applied using a spin coater so as to have a film thickness of 2 μm, and is heated on a hot plate at 80 ° C. for 3 minutes. Preliminary baking was performed to form a coating film. Next, the formed coating film was subjected to main firing at 250 ° C. for 1 hour in a clean oven to form a flattened film.

Forming a Color Filter Protective Film (II) A JSR pigment-based color resist (RG
A substrate having three color filters of red, blue and green (stripe width 100 μm) was formed by B). The surface unevenness of the glass substrate having the color filter was measured by using a surface roughness meter α-step (manufactured by Tencor Corporation) and found to be 1.0 μm. On the glass substrate on which the color filter is formed, the curable composition is applied, pre-baked, and main-baked in the same manner as in the formation of the flattened film (I), whereby the flattened film (I) is formed.
I) was formed.

Evaluation of Protective Film Adhesion In the adhesion test according to JIS K-5400 (1900) 8.5, the flattening film (I) and the flattening film were obtained in accordance with 8.5. In (II), 100 grids were formed with a cutter knife and an adhesion test was performed. Table 1 shows the number of grids peeled off at this time. The adhesion of the protective film (I) was shown as adhesion (I), and the adhesion of the color filter protective film (II) was shown as adhesion (II).

A pencil scratch test was performed on the protective film (I) formed above in accordance with the test method of 8.5.1 among the pencil scratch tests of surface hardness JIS K-5400 (1900) 8.4.
The surface hardness of the protective film was evaluated. Table 1 shows the results.

[0058]Acid resistance Glass substrate on which flattening film (I) formed above is formed
With HCl / FeCl _Two・ H_TwoO / water = 2/1/1 weight ratio
Appearance of flattened film after immersion in aqueous solution at 45 ° C for 15 minutes
The acid resistance of the protective film was evaluated by observing changes in
Was. At this time, those with no change in appearance have good acid resistance
(○), those with peeled or whitened appearance have poor acid resistance
(X).

Alkali Resistance The glass substrate on which the flattening film (I) is formed is immersed in a 5% by weight aqueous solution of sodium hydroxide at 30 ° C. for 30 minutes, and then protected by observing changes in the appearance of the flattening film. The acid resistance of the film was evaluated. At this time, those having no change in appearance were evaluated as having good alkali resistance (（), and those having peeled or whitened appearance were evaluated as poor in alkali resistance (×).

Heat resistance The protective film (I) formed above was measured for thickness using a contact type film thickness measuring device α-step (manufactured by Tencor Japan KK), and then heated at 250 ° C. for 60 minutes in a clean oven. 2
An additional bake at 70 ° C. for 60 minutes was performed. After additional baking,
The film thickness was measured again, and the residual film ratio before and after the additional baking was calculated. Table 1 shows the results.

[0061] The glass substrate having heat discoloration resistance the protective film (I) is formed, to measure the transmission spectrum at a wavelength of 400 to 700 nm. Next, the glass substrate was heated in a clean oven at 250 ° C. for 60 minutes and at 270 ° C. for 60 minutes, and the transmission spectrum at a wavelength of 400 to 700 nm was measured again. The change in the 400 nm transmission spectrum before and after heating was examined, and the heat discoloration resistance was evaluated. 400n before and after heating
Table 1 shows the transmission spectrum of m.

The flatness of the surface of the color filter protective film (II) was measured by a surface roughness meter α-step. Table 1 shows the flattening ratio calculated according to the following equation. Flattening rate = surface unevenness of color filter protective film (II) /
Surface unevenness of color filter before applying protective film x 100

Example 2 The base material obtained in Example 1 was added as component [D] with 4-
The procedure was performed in the same manner as in Example 1 except that 1 part by weight of acetophenyldimethylsulfonium-hexafluoroantimonate was added. Table 1 shows the results.

Example 3 The same operation as in Example 1 was carried out except that the polymer of Synthesis Example 2 was used as the component [A]. Table 1 shows the results.

Example 4 The procedure of Example 2 was repeated except that the polymer of Synthesis Example 2 was used as the component [A]. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that the polymer of Synthesis Example 3 was used as the component [A]. Table 1 shows the results.

Comparative Example 2 The procedure of Example 1 was repeated, except that the polymer of Synthesis Example 4 was used as the component [A]. Table 1 shows the results.

[0068]

[Table 1]

[0069]

According to the curable composition of the present invention, a cured product excellent in heat resistance, flatness and transparency, particularly a color filter protective film excellent in heat resistance and transparency can be produced. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H048 BA02 BA45 BB02 BB14 BB37 BB42 4J036 AD08 AF06 AF07 AF08 AK02 AK03 AK04 AK10 AK11 CA21 CA22 CB08 CB18 DA01 DB15 DB17 DB18 DB20 DB21 DB22 DB23 DB24 EA01 EA03 GA04 EA03 GA21 GA22 GA23 GA29 JA07 JA08 JA15

Claims (4)

[Claims] 1. [A] (a1) a copolymer of an epoxy group-containing monomer, (a2) a copolymer of a maleimide-based monomer and (a3) another monomer, and [B] a polycarboxylic anhydride and a polycarboxylic acid. A curable composition comprising: at least one compound selected from the group; and [C] an epoxy resin different from the component [A]. 2. The curable composition according to claim 1, further comprising [D] an acid generator. 3. Use of the curable composition according to claim 1 or 2 for forming a color filter protective film. 4. A color filter protective film formed from the curable composition according to claim 1.