JP2001064337A - Curable composition and color filter protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition that can give a cured product excellent in heat resistance, the capability of leveling, and transparency by using a copolymer comprising an unsaturated carboxylic acid (anhydride), an epoxy-containing monomer, a maleimide monomer, and other monomers. SOLUTION: This copolymer (A) desirably comprises 5-50 wt.% structural units derived from an unsaturated carboxylic acid and/or an anhydride thereof, 10-70 wt.% structural units derived from an epoxy-containing monomer; 2-50 wt.% structural units derived from a maleimide monomer, and 5-60 wt.% structural units derived from other monomers. The composition may additionally contain (B) a polyfunctional monomer, (C) a radical generator, (D) an epoxy resin different from component A, and (E) an acid generator. The mixing ratio among components B to E is desirably such that 20-150 pts.wt. component B, 1-200 pts.wt. component D, and 0.01-20 pts.wt. component E are present per 100 pts.wt. component A and 0.5-30 pts.wt. component C is present per 100 pts.wt. component B.

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) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride;
This is achieved by a curable composition comprising (a2) a copolymer of an epoxy group-containing monomer, (a3) a maleimide-based monomer, and (a4) a copolymer of other monomers. The curable composition of the present invention may optionally contain [B]
It may further contain a polyfunctional monomer, [C] a radical generator, [D] an epoxy resin different from the above [A] component, and [E] 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] comprises a compound (a1), a compound (a2),
It can be produced by subjecting compound (a3) and compound (a4) to radical polymerization in a solvent in the presence of a polymerization initiator.

[0008] The copolymer "A" used in the present invention comprises a structural unit derived from the compound (a1), preferably 5 units.
-50% by weight, particularly preferably 10-40% by weight. A copolymer in which this constituent unit is less than 5% by weight tends to have reduced heat resistance, chemical resistance and surface hardness. On the other hand, if the copolymer exceeds 40% by weight, the storage stability is reduced.

The compound (a1) includes, for example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids. Of these, acrylic acid,
Methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity and easy availability. These may be used alone or in combination.

The copolymer "A" used in the present invention comprises a structural unit derived from the compound (a2), 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 copolymer tends to decrease. As the epoxy group-containing monomer (a2), the following formula (1)

[0011]

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 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 (a3), 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 (a3),
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 (a4) in an amount of preferably 5 to 60% by weight, particularly preferably 10 to 50% 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 60% by weight, heat resistance and chemical resistance may be insufficient.

Examples of the other monomer component (a4) 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.

Specific 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 weight average molecular weight in terms of polystyrene (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.

Polyfunctional Monomer [B] The polyfunctional monomer [B] used in the present invention includes:
A bifunctional or trifunctional or higher (meth) acrylate is preferably used.

Examples of the above bifunctional (meth) acrylate include ethylene glycol (meth) acrylate,
1,6-hexanediol di (meth) acrylate, 1,
Examples thereof include 9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and bisphenoxyethanol full orange acrylate. Commercially available products include, for example, Aronix M-21
0, M-240, M-6200 (all manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-22
And R-604 (all manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 260, 312 and 335HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

Examples of the trifunctional or higher-functional (meth) acrylate include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. As commercially available products, for example, Aronix M-309, M-400, and M-40
2, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M
-1600, M-1960, M-8100, M-
8530, M-8560, M-9050 (all manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, D
PHA, DPCA-20, DPCA-30, DP
CA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 295, 300, 360
GPT, 3PA, and 400 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.). These bifunctional or trifunctional or higher (meth) acrylates are used alone or in combination.

The amount of the polyfunctional monomer [B] used is
It is generally 10 to 200 parts by weight, preferably 20 to 150 parts by weight, per 100 parts by weight of the component (A). When used in this range, a color filter protective film having an excellent balance between high flatness, adhesion, chemical resistance and heat resistance can be provided.

Radical generator [C] The radical generator [C] used in the present invention is a compound that generates a radical by heat and / or light. Examples of such compounds include biimidazole compounds, benzoin compounds, triazine compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, and azo compounds. Can be. Among these, biimidazole compounds, triazine compounds, acetophenone compounds, and azo compounds are preferred.

The biimidazole compound includes, for example, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,
5'-tetrakis (4-ethoxycarbonylphenyl)
-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, , 2'-bis (2-chlorophenyl) -4,4 ',
5,5′-tetraphenyl-1,2′-biimidazole,
2,2'-bis (2,4-dichlorophenyl) -4,4 ',
5,5′-tetraphenyl-1,2′-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,
4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole and the like can be mentioned.

Of these biimidazole compounds,
Preferred compounds are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4-dichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl -1,
2'-biimidazole, a particularly preferred compound is 2,2'-bis (2,4-dichlorophenyl) -4,4 ',
5,5'-tetraphenyl-1,2'-biimidazole.

Specific examples of the above triazine compounds include 2,4,6-tris (trichloromethyl) -s-
Triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s- Triazine, 2- [2- (furan-2-
Yl) ethenyl] -4,6-bis (trichloromethyl)
-S-triazine, 2- [2- (4-diethylamino-
2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4
-Dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-ethoxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
Triazine compounds having a halomethyl group such as (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine can be mentioned.

Of these triazine compounds, 2-
[2- (3,4-dimethoxyphenyl) ethenyl] -4,
6-Bis (trichloromethyl) -s-triazine is preferred. These triazine compounds can be used alone or in combination of two or more.

Specific examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone. -1, 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,
2-diphenylethan-1-one and the like can be mentioned.

Of these acetophenone compounds,
In particular, 2-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) butanone-1 is preferred. The acetophenone-based compounds can be used alone or in combination of two or more.

Specific examples of the azo compound include 2,2
2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropionitrile), 2,2 ′ -Azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1
-Carbonitrile), 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (1-acetoxy-1-phenylethane) and the like. Among these azo compounds, in particular, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis ( 2-Methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) and the like can be preferably used.

The amount of the radical generator [C] used is usually 0.0 with respect to 100 parts by weight of the polyfunctional monomer [B].
It is 1 to 40 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight.

The curable composition of the present invention may further contain [D] an epoxy resin different from the above-mentioned component [A] and [E] an acid generator, if necessary.

As the epoxy resin different from the component [D] 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 [D] 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] can also be referred to as an epoxy resin, but the epoxy resin of the component [D] has a low molecular weight as compared with the component [A],
They differ in that they are effective in improving the flatness.

Component [E] The acid generator of the component [E] includes a compound that generates an acid by heat and a compound that generates an acid by radiation. Examples of the compound that generates an acid by heat include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. Among them, sulfonium salts and benzothiazonium salts are preferred.

These compounds include, for example, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate,
Acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferably used. These commercial products include Sun Aid
SI-L60, SI-L80, SI-L85, SI-L
100, SI-L110, SI-L145, SI
-L150, SI-L160 (Sanshin Chemical Industry Co., Ltd.)
Manufactured). 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. Further, as the compound generating an acid by radiation, for example, diaryliodonium salts, triarylsulfonium salts and the like can be used.

The diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate,
-Methoxyphenylphenyliodonium trifluoromethanesulfonate or 4-methoxyphenylphenyliodonium trifluoroacetate;

The triarylsulfonium salts include:
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate or 4-phenyl Thiophenyldiphenyltrifluoroacetate can be mentioned as a preferable example.

The proportion of the compound [E] that generates an acid by heat or radiation is preferably 0.01 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, per 100 parts by weight of the component [A]. Parts by weight. When the use ratio of the component [E] is less than 0.01 part by weight based on 100 parts by weight of the component [A], the amount of the acid generated by heating or receiving radiation is small, so that the components [A] and The crosslinking of the component [D] is difficult to proceed sufficiently, and the heat resistance, flatness, chemical resistance, adhesion to a substrate, and the like of the obtained cured film may be reduced. On the other hand, when the use ratio of the component [E] exceeds 20 parts by weight with respect to 100 parts by weight of the component [A], the coating film tends to be rough. In addition, the triazine-based compound in the radical generator [C] can also function as a radiation-sensitive acid generator.

Preparation of Curable Composition The curable composition of the present invention is preferably prepared by uniformly blending the components of the above-mentioned copolymer [A], polyfunctional monomer [B] and radical generator [C]. It is prepared by mixing. 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, a curable composition in a solution state can be prepared by mixing a copolymer [A], a polyfunctional monomer [B], a radical generator [C], and other compounding agents at a predetermined ratio. it can.

As the solvent used for preparing the curable composition of the present invention, the components of the copolymer [A], the polyfunctional monomer [B] and the radical generator [C] are uniformly dissolved. Those that do not react with the components are 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 Kind;
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 methyl ether acetate and propylene Propylene glycol alkyl ether acetates such as glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; propylene glycol methyl ether propionate and propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as pionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and hydroxyacetic acid Methyl, ethyl hydroxyacetate,
Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-butoxypropionate And esters such as propyl 3-butoxypropionate and butyl 3-butoxypropionate.

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 may 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 curable composition of the present invention may contain other components in addition to the above, if necessary, as long as the object of the present invention is not impaired.

Here, as another component, a surfactant for improving coatability can be mentioned. 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. Specific examples thereof include 1,1,2 , 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-hexa) Fluoropentyl) 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, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene Ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxy And a fluorine-based alkyl ester.

[0048] These commercially available products include, for example, B
M-1000, BM-1100 (above, BM CHEM
IE), MegaFac F142D, F172, F173, F183, F178, F191, F191
471 (all manufactured by Dainippon Ink and Chemicals, Inc.), Florad FC 170C, FC-171, FC-430,
FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S
-141, S-145, S-382, SC-10
1, SC-102, SC-103, SC-10
4, SC-105, SC-106 (all manufactured by Asahi Glass Co., Ltd.), F-Top EF301, 303, 35
2 (Shin-Akita Chemical Co., Ltd.)
-100, FT-110, FT-140A, FT
-150, FT-250, FT-251, FTX
-251, FTX-218, FT-300, FT
-310, FT-400S (above, manufactured by Neos Co., Ltd.)
And the like. Examples of the silicone-based surfactant include Toray silicone DC3PA and D-silicone.
C7PA, SH11PA, SH21PA, SH2
8PA, SH29PA, SH30PA, SH-1
90, SH-193, SZ-6032, SF-8
428, DC-57, DC-190 (all manufactured by Toray Silicone Co., Ltd.), TSF-4440, TSF-43
00, TSF-4445, TSF-4446, TSF-
4460 and TSF-4452 (both manufactured by Toshiba Silicone Co., Ltd.).

In addition, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Ethylene aryl ethers; Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Made),

(Meth) acrylic acid copolymer Polyflow Nos. 57 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. These surfactants are copolymers [A]
It is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight. When the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

An adhesion aid may be used to improve the adhesion to the substrate. As such an adhesion aid, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such an adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion aid exceeds 20 parts by weight, heat resistance tends to decrease. The composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

Method for Forming Color Filter Protective Film Next, a method for forming the color filter protective film of the present invention using the curable composition of the present invention will be described in detail. The curable composition of the present invention can be suitably used for forming a color filter protective film, and such use has not been known so far. The coating film is formed by applying the curable composition solution of the present invention to the surface of the color filter on the substrate and removing the solvent by heating. As a method for applying the curable composition solution to the surface of the color filter, various methods such as a spray method, a roll coating method, and a spin coating method can be adopted.

Next, the coating film is heated (prebaked). By heating, the solvent is volatilized, and a coating film having no fluidity is obtained. The heating conditions vary depending on the type of each component, the mixing ratio, etc.
It can be used in a wide range of about 0 to 600 seconds. In addition,
When a conventional protective film is formed by a photolithography method, prebaking conditions are usually 70 to 90 ° C.,
A condition of about 0 to 300 seconds is employed. Therefore, as a pre-bake condition when forming the protective film of the present invention using the curable composition of the present invention, there is an advantage that the conventional protective film forming process can be employed as it is without changing any conditions. .

Next, the heated coating film is irradiated with radiation through a mask having a predetermined pattern, and then developed with a developing solution.
Remove unnecessary parts. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine; Secondary amines such as -n-propylamine; triethylamine,
Tertiary amines such as methyldiethylamine and N-methylpyrrolidone; alcoholamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline; Piperidine, 1,8-diazabicyclo [5.4.
0] -7-undecene, 1,5-diazabicyclo [4.
3.0] -5-nonane or the like can be used. Further, an aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like to the above-mentioned alkaline aqueous solution can also be used as a developer.

The development time is usually 30 to 180 seconds. Further, the developing method may be any of a puddle method and a dipping method. After the development, the substrate is washed with running water for 30 to 90 seconds and air-dried with compressed air or compressed nitrogen to remove moisture on the substrate and form a patterned film. Subsequently, by a heating device such as a hot plate and an oven, at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time,
For example, by performing a heat treatment on a hot plate for 5 to 30 minutes and in an oven for 30 to 90 minutes, a patterned crosslinked film can be obtained. In the present invention, "radiation" refers to visible light, ultraviolet light, far ultraviolet light,
Includes radiation, electron beams, etc.

[0056]

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 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether. Successively, 18 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 22 parts by weight of N-phenylmaleimide were charged and replaced with nitrogen, and then gentle stirring was started. 70 ℃ of solution temperature
, And the temperature was maintained for 3 hours to obtain the copolymer [A-
1] was obtained. The solid content concentration of the obtained polymer solution was 30.8% by weight.

Synthesis Example 2 A flask equipped with a condenser and a stirrer was charged with 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 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. Solution temperature 7
0 ° C., this temperature was maintained for 3 hours, and the copolymer [A
-2] was obtained. The solid content concentration of the obtained polymer solution was 30.1% by weight.

Synthesis Example 3 A flask equipped with a condenser and a stirrer was charged with 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 20 parts by weight of dicyclopentanyl methacrylate were charged and replaced with nitrogen, and then gentle stirring was started. The solution temperature was raised to 70 ° C., and this temperature was maintained for 3 hours to obtain a polymer solution containing the copolymer [A-3]. The solid content concentration of the obtained polymer solution was 30.5% by weight.

Example 1 Preparation of Thermosetting Resin Composition The polymer solution (copolymer [A-1] 10) obtained in Synthesis Example 1
0 parts by weight (solid content)) and K as component [B]
80 parts by weight of AYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) and IRGACURE-819 as a component [C] (bis (2,4,6-trimethylbenzoyl manufactured by Ciba Specialty Chemicals) ) -Phenylphosphine oxide), 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and 0.1 part by weight of SH-28PA (manufactured by Toray Silicone Co., Ltd.) as a surfactant. After mixing and dissolving in diethylene glycol dimethyl ether so as to have a solid concentration of 28% by weight, the mixture was filtered through a 0.5 μm-pore-size millipore filter to prepare a thermosetting resin composition solution (S-1). did.

Forming the flattening film (I) The curable composition (S-1) is applied on a glass substrate by using a spin coater so as to have a thickness of 2 μm, and is then heated on a hot plate at 80 ° C. for 3 minutes. Preliminary firing was performed under the conditions described above to form a coating film. This coating film was irradiated with ultraviolet light having an intensity of 10 mW / cm ² at 365 nm for 30 seconds using a predetermined pattern mask. This ultraviolet irradiation was performed in air. The main baking was performed at 250 ° C. for 1 hour in a clean oven to form a flattening film.

Forming a flattening film (II) On a glass substrate, 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 Adhesion of Flattening Film In the adhesion test according to JIS K-5400 (1900) 8.5, the flattening film (I) and flattening were performed according to the 8.5-2 grid tape method. An adhesion test was performed by forming 100 grids on the film (II) with a cutter knife. Table 1 shows the number of grids peeled off at this time. The adhesion of the flattening film (I) is shown as adhesion (I), and the adhesion of the flattening film (II) is shown as adhesion (II).

Surface Hardness In the pencil scratch test of JIS K-5400 (1900) 8.4, a pencil scratch test was performed on the flattened film (I) formed above in accordance with the test method of 8.5.1. Then, the surface hardness of the flattening film was evaluated. Table 1 shows the results
Shown in

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) has been formed is immersed in a 5% by weight aqueous sodium hydroxide solution 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 light-scattering film formed above was measured with a contact type film thickness measuring device α-step (manufactured by Tencor Japan Co., Ltd.) and then heated at 250 ° C. for 60 minutes in a clean oven. An additional bake was performed. After the additional baking, the film thickness was measured again, and the film reduction rate before and after the additional baking was calculated. Table 1 shows the results.

The glass substrate on which the flattening film (I) was formed was
The transmission spectrum at a wavelength of 400 to 700 nm was measured. Next, the glass substrate was heated in a clean oven at 250 ° C. for 60 minutes, and then the wavelength of 400 to 7 was again applied.
The transmission spectrum at 00 nm was measured. The change in the 400 nm transmission spectrum before and after heating was examined, and the heat discoloration resistance was evaluated. Table 1 shows the rate of change of the transmission spectrum at 400 nm before and after heating.

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

Example 2 In Example 1, KAYARAD was used as the component (B).
Except that Aronix TO-1450 was used instead of DPHA, a composition solution (S-2) was prepared in the same manner as in Example 1.
Was prepared and evaluated. Table 1 shows the results.

Example 3 The procedure of Example 1 was repeated, except that the solution containing the copolymer [A-2] obtained in Synthesis Example 2 was used instead of the solution containing the copolymer [A-1]. Composition solution (S-
3) was prepared and evaluated. Table 1 shows the results.

Comparative Example 1 The procedure of Example 1 was repeated, except that the solution containing the copolymer [A-3] obtained in Synthesis Example 3 was used instead of the solution containing the copolymer [A-1]. Composition solution (S-
4) was prepared and evaluated. Table 1 shows the results.

[0073]

[Table 1]

[0074]

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) 2H025 AA00 AA10 AA18 AB13 AD01 BC35 BC42 BC83 BE00 CA00 CB30 2H048 BA48 BB37 4J027 AA02 AD03 AE01 AE02 BA05 BA06 BA07 BA08 BA09 BA13 BA14 BA16 BA19 BA20 BA21 BA24 BA26 CB03 CB03 CB03 CB03 CB03 CB03 CB03

Claims (5)

[Claims] [A] A copolymer of (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (a2) an epoxy group-containing monomer, (a3) a maleimide monomer and (a4) another monomer A curable composition comprising: 2. The curable composition according to claim 1, further comprising [B] a polyfunctional monomer and [C] a radical generator. 3. The composition according to claim 1, further comprising [D] an epoxy resin different from the component [A] and [E] an acid generator.
Or the curable composition according to 2. 4. Use of the curable composition according to claim 1 for forming a color filter protective film. 5. A color filter protective film formed from the curable composition according to claim 1.