KR20010070042A - Curable composition and color filter protective film - Google Patents

Abstract

PURPOSE: A curable composition and a color filter protective film are provided, which is excellent in heat resistance, flatness and transparency, especially a film for protecting a color filter, excellent in the heat resistance and the transparency. CONSTITUTION: This curable composition comprises £A|unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride(a1), a monomer containing an epoxy group(a2), a maleimide-based monomer(a3) and other monomer copolymers,£B|a multifunctional monomer, and £C|a radical genetor.

Description

Curable Composition and Color Filter Protective Film

The present invention relates to a curable composition and a color filter protective film. More specifically, the cured product excellent in heat resistance and transparency can be provided, and for this reason, it is related with the curable composition and color filter protective film suitable for formation of a color filter protective film.

The color liquid crystal display device of the super twisted nematic (STN) method is manufactured through the process of making a transparent electrode film on a color filter protective film, and forming a liquid crystal aligning film thereon. In that case, since it heats in the process of forming a transparent electrode film and the process of forming a liquid crystal aligning film, when the temperature of a protective film rises to 250 degreeC or more, and heat resistance of a protective film is not enough, a vaporization by-product evaporates from a protective film in a transparent electrode film. Invasion occurs to increase the resistance of the transparent electrode film, thereby reducing conduction, or the protective film itself is colored, thereby decreasing transparency.

Conventionally, as a raw material of a protective film, the copolymer etc. of Unexamined-Japanese-Patent No. 6-157716 were known, but such a copolymer had the problem to be solved as mentioned above.

It is an object of the present invention to provide a curable composition that provides a cured product excellent in heat resistance, planarization and transparency.

Another object of the present invention is to provide a color filter protective film excellent in heat resistance and transparency formed from the curable composition of the present invention.

According to the present invention, the above object of the present invention is firstly determined by [A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing monomer, (a3) maleimide monomer and (a4). ) And a curable composition containing a copolymer of other monomers, a [B] polyfunctional monomer and a [C] radical generator.

The said curable composition can further contain the epoxy resin and [E] acid generator different from [D] the said [A] component as needed.

The above object of the present invention is a copolymer of [A '] (a2) epoxy group-containing monomer, (a3) maleimide monomer and (a4) other monomer, [F] polyhydric carboxylic anhydride and polyhydric carboxylic acid It is achieved by the curable composition characterized by containing at least 1 sort (s) of compound chosen from the group which consists of an epoxy resin different from [D '] and the said [A'] component.

Said curable composition can further contain an [E '] acid generator as needed. Still another object and advantage of the present invention are achieved by a color filter protective film formed by the curable composition of the present invention.

Hereinafter, each component of the curable composition of this invention is demonstrated in detail.

The 1st aspect of this invention is [A] of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group containing monomer, (a3) maleimide-type monomer, and (a4) other monomers. It is a curable composition containing a copolymer, a [B] polyfunctional monomer, and a [C] radical generator.

Said curable composition can further contain the epoxy resin and [E] acid generator different from [D] the said [A] component as needed.

Copolymer [A]

Copolymer [A] can be produced by radical polymerization of compound (a1), compound (a2), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent.

The copolymer "A" used in the present invention preferably contains 5 to 50% by weight, particularly preferably 10 to 40% by weight of the structural unit derived from the compound (a1). Copolymers having this structural unit of less than 5% by weight tend to lower heat resistance, chemical resistance and surface hardness. On the other hand, when the copolymer exceeds 40% by weight, the storage stability is lowered.

As a compound (a1), 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 such dicarboxylic acids. Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity and availability. These are used alone or in combination.

The copolymer "A" used in the present invention preferably contains 10 to 70% by weight, particularly preferably 20 to 60% by weight of the structural unit derived from the compound (a2). The copolymer whose structural unit is less than 10 weight% tends to lower the heat resistance and surface hardness of the protective film obtained. On the other hand, when it exceeds 70 weight%, there exists a tendency for the storage stability of a copolymer to fall.

As an epoxy group containing monomer (a2), the compound represented by following General formula (1) is mentioned.

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, m is a number from 1 to 8,

In 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 either linear or branched, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert. -Butyl group and n-pentyl group are mentioned. R ² is a hydrogen atom, a methyl group or an ethyl group.

As a monomer represented by the said General formula (1), (meth) glycidyl (meth) acrylate, the glycidyl (alpha)-ethylacrylate, the glycidyl (alpha)-n-propyl acrylate, the glycidyl (alpha)-n-butylacrylate, (meth ) Acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-4,5-epoxypentyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, (meth) acrylic acid Methyl glycidyl etc. are mentioned. Among these, glycidyl (meth) acrylate is particularly preferable. These monomers can be used individually or in combination of 2 or more types.

The copolymer "A" used in the present invention preferably contains 2 to 50% by weight, particularly preferably 5 to 40% by weight of the structural unit derived from the compound (a3). When this structural unit is less than 2 weight%, there exists a tendency for heat resistance, chemical-resistance, and surface hardness to fall. When this structural unit exceeds 50 weight%, there exists a tendency for the film-forming property of a coating film to fall.

As maleimide-type monomer (a3), N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl-4- maleim Midbutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide. These can be used individually or in combination of 2 or more types.

The copolymer [A] used in the present invention preferably contains 5 to 60% by weight, particularly preferably 10 to 50% by weight of structural units derived from other monomers (a4). When this structural unit is less than 5 weight%, the film-forming property of a coating film may run short, and when this structural unit exceeds 60 weight%, heat resistance or chemical resistance may fall.

As such other monomer component (a4), For example, alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.O ^2,6 ] decan-8-yl methacrylate (referred to in the art as dicyclopentanyl methacrylate) ), Methacrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl methacrylate and isoboroyl methacrylate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl acrylate (common name in the art as dicyclopentanyl acrylate), dicyclo Acrylic cyclic alkyl esters such as fentanyloxyethyl acrylate and isoboroyl acrylate: methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid diesters such as acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate, diethyl maleate, diethyl fumarate and diethyl itaconate; 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.

Among them, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl meta Acrylate, tricyclo [5.2.1.O ^2,6 ] decane-8-yl acrylate, 1,3-butadiene and the like are preferred in terms of copolymerization reactivity. These are used alone or in combination.

As a preferable specific example of copolymer [A], (meth) acrylic acid / (meth) acrylic-acid glycidyl / N-phenylmaleimide / styrene copolymer, (meth) acrylic acid / (meth) acrylic acid glycidyl / N-cyclohexyl Maleimide / styrene copolymer, (meth) acrylic acid / (meth) acrylic acid glycidyl / N-phenylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate Copolymer, (meth) acrylic acid / (meth) acrylate glycidyl / N-cyclohexylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate copolymer Can be mentioned.

As a solvent used for manufacture of copolymer [A], For example, Alcohol, 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 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 and diethylene glycol ethyl methyl ether; Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol monoalkyl ethers of propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate Propylene glycol alkyl ether acetates such as these; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate 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-pentanane; And methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyacetic acid Ethyl, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, pro Methyl acetate, propoxy acetate, propyl acetate, propoxy acetate, butyl acetate, methyl butoxy acetate, butoxy acetate, butoxy Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionate, Ester, such as butyl 3-butoxy propionate, is mentioned.

As a polymerization initiator used for manufacture of copolymer [A], what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- Azo compounds such as (2,4-dimethylvaleronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile): benzoyl peroxide, lauroyl peroxide, t Organic peroxides such as -butyl peroxy pibarate and 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, you may use a peroxide together with a reducing agent as a redox type initiator.

The copolymer used in the present invention, [A] is, in terms of polystyrene (hereinafter referred to as "Mw") having a weight average molecular weight, usually 2 × 1O ³ to ⁵ × 1O 5, preferably from 5 × 1O ³ to 1 × 1O It is preferable that it is ^five . If Mw is less than 2x10 <^3> , the film obtained will tend to reduce heat resistance and surface hardness. On the other hand, when it exceeds 5 * 10 < ⁵ >, flattening property will fall.

Multifunctional Monomer [B]

As the polyfunctional monomer [B] used in the present invention, bifunctional or trifunctional or higher (meth) acrylates are preferably used.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned. As the commercial item, for example, Alonics M-210, copper M-240, copper M-6200 (above, product of Toagosei Co., Ltd.), KAYARAD HDDA, copper HX-220, copper R-604 (more, Nippon Kaya Co., Ltd.), biscot 260, copper 312, copper 335 HP (above, Osaka Yugaku Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said trifunctional or more than (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra ( Meth) acrylate, dipentaerythritol pen evening (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. As the commercial item, for example, Alonics M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M -1310, East M-1600, East M-1960, East M-8100, East M-8530, East M-8560, East M-9050 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120 (above, Nippon Kayaku Co., Ltd.), biscot 295, copper 300, copper 360, copper GPT, copper 3 PA, copper 400 ( As mentioned above, Osaka Yuki Kagaku Kogyo Co., Ltd.) etc. are mentioned.

These bifunctional or trifunctional or more than (meth) acrylates can be used individually or in combination.

The usage-amount of a polyfunctional monomer [B] is 10-200 weight part normally per 100 weight part of [A] component, Preferably it is 20-150 weight part. In the use of this range, it is possible to provide a color filter protective film excellent in the balance between high flattening property, adhesion, chemical resistance and heat resistance.

Radical Generator [C]

As radical generating agent [C] used by this invention, it is a compound which generate | occur | produces 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, azo compounds, and the like. . Among these, a biimidazole type compound, a triazine type compound, an acetophenone type compound, and an azo type compound are preferable.

As said biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2'-, for example. Biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,

2,2'-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'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

Among these biimidazole compounds, preferred compounds are 2,2'-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, particularly preferred compounds are

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

Moreover, as a specific example of the said triazine type compound,

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,

And triazine-based compounds having halomethyl groups, such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.

Among these triazine compounds,

Preference is given to 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine.

These triazine type compounds can be used individually or in mixture of 2 or more types.

As a specific example of the said acetophenone type compound,

2-hydroxy-2-methyl-1-phenylpropan-1-one,

2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexylphenylketone,

2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one etc. are mentioned.

Among these acetophenone compounds, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 is particularly preferable.

The said acetophenone type compound can be used individually or in mixture of 2 or more types.

Specific examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (4-dimethylvaleronitrile), and 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), etc. are mentioned.

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. have.

The use amount of the radical generator [C] is usually 0.01 to 40 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight based on 100 parts by weight of the polyfunctional monomer [B].

[D] component

As an epoxy resin different from [A] component, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, etc. can be used, for example. These can be obtained as a commercial item. For example, as bisphenol A type epoxy resin, epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, Yuka Shell Epoxy Co., Ltd.), etc. As the epoxy resin, Epicoat 807, Copper 834 (above, manufactured by Yuka Shell Epoxy), and the like, and Epiphenol 152, Copper 154, Copper 157H65 (above, manufactured by Yuka Shell Epoxy) , EPPN 201, copper 202 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like, as the cresol novolak type epoxy resin, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027. (Above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.), and the like as other cyclic aliphatic epoxy resins, CY175, CY177, CY179 (above, CIBA-GEIGY A.G) , ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above, manufactured by UCC Corporation), Shodine 509 (product of Showa Denko Corporation), Araldite CY-182, Copper CY-192, Copper CY-184 (above, made in CIBA-GEIGY AG Product), Epiclone 200, copper 400 (more than, Dai Nippon Ink Industries Co., Ltd.), epicoat 871, copper 872, EP1032H60 (more, Yuka shell epoxy), ED-5661, ED-5662 ( As described above, Cerani Coating Co., Ltd. is used as an aliphatic polyglycidyl ether. Epicoat 190P, copper 191P (above, Yuka Shell Epoxy Co., Ltd.), Eporite 100 MF (Kyoeisha Chemical Co., Ltd.) ), Epiol TMP (manufactured by Yushi Corp., Japan), and the like.

Among these, bisphenol-A epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin are mentioned as a preferable thing.

The use ratio of epoxy resin [D] is 1-200 weight part per 100 weight part of components [A], More preferably, it is 3-100 weight part.

Moreover, although component [A] can also be called an epoxy resin, the epoxy resin of component [D] is a low molecular weight body compared with component [A], and differs in that it is effective in the improvement of planarization property.

[E] component

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.

As a compound which generate | occur | produces an acid by heat, onium salts, such as a sulfonium salt, a benzothiazonium salt, an ammonium salt, and a phosphonium salt, are used. Especially, a sulfonium salt and a benzothiazonium salt are preferable.

As a specific example of the said sulfonium salt, 4-acetophenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium hexafluoro alsenate, dimethyl-4- (benzyloxycarbonyloxyphenyl sulfonium hexafluoro Roantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroalsenate, dimethyl-3-chloro-4-acetoxy Alkylsulfonium salts such as phenylsulfonium hexafluoroantimonate,

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroalsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl 4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroalsenate, dibenzyl-3-methyl-4-hydroxy-5-tert Dibenzylsulfonium salts such as butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenyl Methylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzylsulfonium salts such as antimonate and o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate;

And sulfonium salts represented by the following formulas (2) to (8).

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxybenzyl Benzylbenzothiazo such as benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobensothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobensothiazonium hexafluoroantimonate A tan salt is mentioned.

Among them, 4-acetoxyphenyldimethylsulfonium hexafluoroalsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylphenylmethylsulfonium hexafluoroantimonate, Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylpenylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferably used. . Examples of such commercially available products include Sunaid SI-L85, SI-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Kagaku Kogyo Co., Ltd.).

The compound which generate | occur | produces an acid by such heat can also function as a compound which generate | occur | produces an acid by radiation.

These compounds can be used individually or in combination of 2 or more types.

Moreover, as a compound which generate | occur | produces an acid by radiation, diaryl iodonium salt, triaryl sulfonium salt, etc. can be used, for example.

As diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, or 4-methoxyphenylphenyl iodonium tri Fluoroacetates;

Examples of the triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenyldiphenylsulfonate. Phenium trifluoro acetate, 4-phenylthio phenyl diphenyl trifluoro methanesulfonate, or 4-phenylthio phenyl diphenyl trifluoro acetate are mentioned as a preferable thing, respectively.

The use ratio of the compound [E] which 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 based on 100 parts by weight of the component [A].

When the use ratio of component [E] is less than 0.01 weight part with respect to 100 weight part of component [A], since the amount of acid which arises by receiving heating or radiation is small, bridge | crosslinking of component [A] and component [D] It is difficult to fully advance, and the heat resistance, planarization property, chemical resistance, adhesiveness with a board | substrate, etc. of the cured film obtained may fall. On the other hand, when the use ratio of component [E] exceeds 20 weight part with respect to 100 weight part of components [A], coarseness will arise in a coating film easily.

Moreover, the triazine type compound in radical generator [C] can function also as a radiation sensitive acid generator.

Other Formulations

In the 1st aspect of the curable composition of this invention, you may contain other compounding agents other than the above as needed in the range which does not impair the objective of this invention.

As another compounding agent, a silane coupling agent, surfactant, etc. are mentioned, for example.

[Silane Coupling Agent]

A silane coupling agent is used in order to improve adhesiveness with a cured film and a base, and the functional silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is used preferably. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. Such 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, the heat resistance tends to be lowered.

[Surfactants]

Surfactant is used in order to improve applicability | paintability, A fluorochemical surfactant and silicone type surfactant can be used suitably.

As the fluorine-based surfactant, a compound having a fluoroalkyl or a fluoroalkylene group can be suitably used in at least one site of the terminal, the main chain and the side chain, and 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-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1, 1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylic acid, fluoroalkylpolyoxyethylene ether, digly Serine tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, pafluoroalkylpolyoxyethanol, pafluoroalkylalkoxylate, fluorine Alkyl ester etc. are mentioned.

Moreover, as these commercial items, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE Co., Ltd.), Megapack F142D, East F172, East Fl73, East Fl83, East F178, East Fl91, East F471 Dainippon Ink & Chemicals Co., Ltd.), Floroid FC170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, Copper S-113 , S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Above, Asahi Glass Co., Ltd.), F-top EF301, copper 303, copper 352 (above, Shin-Aki Takasei Co., Ltd.), butadient FT-100, copper FT-110, copper FT-140A, Copper FT-150, copper FT-250, copper FT-251, copper FTX-251, copper FTX-218, copper FT-300, copper FT-310, copper FT-400S (above) Can be mentioned. Moreover, as silicone type surfactant, for example, tresilicon DC3PA, copper DC7PA, copper SH11PA, copper SI-121PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428, copper DC-57, copper DC-190 (above, manufactured by Toray Silicon, Inc.), TSF-444Q, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (more, What is marketed by brand names, such as Toshiba Silicone Co., Ltd., are mentioned.

In addition, polyoxyethylene, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, etc. Nonionic surfactants such as polyoxyethylene dialkyl esters such as aryl ethers, polyoxyethylene dilaurate and polyoxyethylene distearate; And organosiloxane polymers KP34l (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid copolymer polyflow Nos. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

Such surfactant is preferably used in an amount of 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant exceeds 5 parts by weight, film roughness easily occurs during application.

The 2nd aspect of this invention is a copolymer of a [A '] (a2) epoxy group containing monomer, (a3) maleimide-type monomer, and (a4) other monomer, [F] polyhydric carboxylic anhydride, and polyhydric carboxylic acid It is a curable composition containing at least 1 sort (s) of compound chosen from the group which consists of these, and an epoxy resin different from [D '] the said [A'] component.

Said curable composition can further contain an [E '] acid generator as needed.

Copolymer [A ']

Copolymer [A '] can be manufactured by radically polymerizing a compound (a2), a compound (a3), and a compound (a4) in a solvent in presence of a polymerization initiator.

Here, the compound (a2), the compound (a3), and the compound (a4) can use what was illustrated about copolymer [A].

The copolymer [A '] used in the present invention contains a structural unit derived from the compound (a2), preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. The copolymer whose structural unit is less than 10 weight% tends to lower the heat resistance and surface hardness of the protective film obtained. On the other hand, when it exceeds 70 weight%, there exists a tendency for the storage stability of curable composition to fall.

The copolymer [A '] used in the present invention contains a structural unit derived from the compound (a3), preferably 2 to 50% by weight, particularly preferably 5 to 40% by weight. When this structural unit is less than 2 weight%, there exists a tendency for heat resistance, chemical-resistance, and surface hardness to fall. When this structural unit exceeds 50 weight%, there exists a tendency for the film-forming property of a coating film to fall.

The copolymer [A '] used in the present invention preferably contains 5 to 80% by weight, particularly preferably 10 to 70% by weight of the structural unit derived from the other monomer (a4). When this structural unit is less than 5 weight%, the film-forming property of a coating film may become inadequate, and when this structural unit exceeds 80 weight%, heat resistance or chemical resistance may be insufficient.

As a preferable specific example of a copolymer [A '], (meth) acrylic-acid glycidyl / N-phenylmaleimide / styrene copolymer, (meth) acrylic-acid glycidyl / N-cyclohexyl maleimide / styrene copolymer, (meth ) Glycidyl acrylate / N-phenylmaleimide / styrene / tricyclo [5.2.1. O ^2,6 ] decane-8-yl (meth) acrylate copolymer, glycidyl (meth) acrylate / N-cyclohexylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8 -Yl (meth) acrylate copolymer is mentioned.

As a solvent used for manufacture of copolymer [A '], the thing illustrated about copolymer [A] can be used.

Moreover, what was illustrated about copolymer [A] can be used as a polymerization initiator used for manufacture of copolymer [A '].

As for the copolymer [A '] used by this invention, the polystyrene conversion weight average molecular weight (henceforth "Mw") is 2x10 <^3> -5 * 10 <^5> , Preferably it is 5x10 <^3> -1 *. It is preferred that it is 10 ⁵ . If Mw is less than 2x10 <^3> , the film obtained will tend to fall in heat resistance and surface hardness. On the other hand, when it exceeds 5 * 10 < ⁵ >, flattening property will fall.

[F] ingredients

The polyhydric carboxylic anhydride or polyhydric carboxylic acid used as the component [F] acts as a curing agent for the component [A '].

Specific examples of the polyhydric carboxylic acid anhydride include itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hymic anhydride. Aliphatic dicarboxylic acid anhydrides; Alicyclic polyhydric carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; Aromatic polyhydric carboxylic acid anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; Ester group-containing acid anhydrides such as ethylene glycolbis anhydrous trimellitate and glycerin tris anhydrous trimellitate. Among these, use of aromatic polyhydric carboxylic anhydride, especially trimellitic anhydride, is preferable at the point from which the cured film with high heat resistance is obtained.

Moreover, as a specific example of polyhydric carboxylic acid, aliphatic polyhydric carboxylic acid, such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid, itaconic acid, hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid Alicyclic polyhydric carboxylic acids such as 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid; And aromatic polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and 1,2,5,8-naphthalenetetracarboxylic acid. In these, aromatic polyhydric carboxylic acid is suitable from a viewpoint of the reactivity of a curable composition, the heat resistance of the cured film formed, etc.

Such polyhydric carboxylic anhydride and polyhydric carboxylic acid can be used individually or in combination of 2 or more types.

The use ratio of the component [F] is usually 1 to 100 parts by weight, more preferably 10 to 70 parts by weight with respect to 100 parts by weight of the [A '] component. When the ratio of component [F] is less than 1 weight part, the cured film which has a sufficiently high crosslinking density is hard to be obtained, and the various tolerances of the cured film may fall. On the other hand, when the ratio of [F] component exceeds 100 weight part, unreacted component [F] is easy to remain in a large amount in the cured film obtained, As a result, the property of the cured film becomes unstable, The adhesiveness of a cured film may fall.

[D '] component

As an epoxy resin different from [A '] component, what was illustrated as [D] component can be used.

The use ratio of epoxy resin [D '] is 100 weight part of components [A'], Preferably it is 1-200 weight part, More preferably, it is 3-100 weight part.

Moreover, component [A '] is also an epoxy resin, The epoxy resin of component [D'] is a low molecular weight compared with component [A '], and differs in that it is effective in the improvement of planarization property.

[E '] component

As the acid generator [E '], a compound which generates an acid by heat can be used among those exemplified as the component [E].

The use ratio of acid generator [E '] becomes like this. Preferably it is 0.01-20 weight part with respect to 100 weight part of [A'] component, More preferably, it is 0.2-10 weight part.

When the use ratio of the component [E '] is less than 0.01 part by weight with respect to 100 parts by weight of the component [A'], since the amount of acid generated by heating is small, the amount of the component [A '] and the component [D'] Crosslinking hardly advances enough, and the heat resistance of the cured film obtained, planarization property, chemical resistance, adhesiveness with a board | substrate, etc. may fall. On the other hand, when it exceeds 20 weight part with respect to 100 weight part of use ratios [A '] component of a component [E'], coarseness becomes easy to arise in a coating film.

Other Formulations

In the 2nd aspect of the curable composition of this invention, you may contain other compounding agents other than the above as needed in the range which did not impair the objective of this invention.

As another compounding agent, a silane coupling agent, a hardening accelerator, surfactant, a ultraviolet absorber, etc. are mentioned, for example.

[Silane Coupling Agent]

A silane coupling agent is used in order to improve the adhesiveness of a cured film and the gas which should form this, and the silane coupling agent illustrated about the 1st aspect of this invention can be used.

The use ratio of a silane coupling agent becomes like this. Preferably it is 100 weight part or less with respect to 100 weight part of components [A '], More preferably, it is 0.1-100 weight part, Especially preferably, it is 1-40 weight part. When the use ratio of a silane coupling agent is less than 0.1, the effect which provides sufficient adhesiveness between a cured film and the gas which should form this may not be acquired. On the other hand, when the use ratio of a silane coupling agent exceeds 100 weight part, the alkali resistance, solvent resistance, etc. of the cured film obtained may fall.

[Hardening accelerator]

A hardening accelerator is used in order to accelerate | stimulate reaction with a [A '] component and a [F] component, ie, a hardening | curing agent, Generally, the compound which has a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom is used. do.

Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole or isocyanuric acid or 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' '-diaminotriadiinyl) Imidazole derivatives such as ethyl] imidazole and benzimidazole are suitable, and most preferably 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methyl Imidazole and the like.

These compounds can be used alone or in combination of two or more as a curing accelerator.

The curing accelerator is used in an amount of preferably 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 '].

[Surfactants]

Surfactant is used in order to improve applicability | paintability, The thing illustrated about the 1st aspect of this invention can be used.

Although the use ratio of surfactant changes also with the kind or ratio of each component which comprises the kind or curable composition, etc., Preferably it is 0-10 weight part with respect to 100 weight part of component [A '], More preferably, It is used in the range of 0.0001 to 5 parts by weight.

Preparation of Curable Compositions

The curable composition of the present invention is advantageously dissolved in a suitable solvent and used in a solution state. For example, in the case of the 1st aspect of this invention, a copolymer [A], a polyfunctional monomer [B], a radical generator [C], and the epoxy resin [D] optionally added, and other compounding agents, By mixing in a predetermined ratio in a solvent, the curable composition of a solution state can be manufactured.

Moreover, in the case of the 2nd aspect of this invention, a copolymer [A '], a component [F], an epoxy resin [D'], the component [E] added arbitrarily, and other compounding agents are prescribed | regulated in a solvent. By mixing at the ratio of, the curable composition in a solution state can be produced.

As a solvent used for manufacture of the curable composition of this invention, For example, Alcohol, 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 acetates, such as methyl cellosolve acetate and an ethyl cellosolve acetate, and diethylene glycol mono Diethylene glycols such as methyl 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 ether, and propylene Propylene glycol alkyl ether acetates such as glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, and propylene glycol Propylene glycol alkyl ether acetates such as colethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate, aromatic hydrocarbons such as toluene and xylene, methyl ethyl ketone, cyclohexanone, 4 Ketones such as hydroxy-4-methyl-2-pentanane and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate and 2-hydroxy Ethyl hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate, 3-hydroxyethyl propionate, 3 Propyl hydroxypropionate, methyl 3-hydroxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate Of the esters may be mentioned.

Among these solvents, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycols are preferably used because of their solubility, reactivity with each component, and easy formation of a coating film.

Moreover, a high boiling point solvent can also be used together with the said solvent. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Rollidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate And diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

In addition, the composition solution prepared as described above may be used after being filtered using a Millipore filter or the like having a pore diameter of about 0.5 μm.

The concentration of the curable composition in the composition solution is not particularly limited and can be appropriately selected depending on the intended use. The concentration of solids is preferably 1 to 60% by weight, more preferably 5 to 40% by weight.

Formation method of color filter protective film

By using the curable composition of this invention, a cured film can be formed as follows, for example.

The curable composition of this invention can be used suitably for formation of a color filter protective film, It is not known conventionally to use it as such.

When using the curable composition of the 1st aspect of this invention, a color filter protective film can be formed as follows.

First, the coating film is formed by apply | coating the curable composition solution of this invention to the color filter surface on a board | substrate, and removing a solvent by heating. As a coating method of the curable composition solution to a color filter surface, various methods, such as a spray method, a roll coat method, and a spin coating method, can be employ | adopted, for example.

Next, this coating film is heated (prebaked). By heating, a solvent volatilizes and the coating film without fluidity is obtained.

Although heating conditions are different also according to the kind of each component, a compounding ratio, etc., it can be used in 60-120 degreeC and the wide range about 10 to 600 second normally.

Moreover, when forming a conventional protective film by the port lithography method, the conditions of 70-90 degreeC and about 30 to 300 second are used normally as a prebaking condition. Therefore, as a prebaking condition at the time of forming the protective film of this invention using the curable composition of this invention, there exists an advantage that the conventional protective film formation process can be employ | adopted as it is, without changing conditions at all.

Subsequently, the heated coating film is irradiated with radiation through a mask of a predetermined pattern, and then unnecessary portions are removed with a developer.

As a developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone, alcohol amines such as dimethylethanolamine and triethanolamine; Quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; Alkali which consists of alkalis of cyclic amines, such as a pyrrole, a piperidine, 1,8- diazabicyclo [5.4.0] -7-undecene, and a 1, 5- diazabicyclo [4.3.0] -5-nonane An aqueous solution can be used.

Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. to the said aqueous alkali solution can also be used as a developing solution.

The developing time is usually 30 to 180 seconds. In addition, any of a developing method may be sufficient as the sticking method and the dipping method. After the development, flowing water washing is performed for 30 to 90 seconds, and air dried with compressed air or compressed nitrogen to remove moisture on the substrate to form a patterned film. Subsequently, a heating device such as a high temperature plate or an oven is heated at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, on a high temperature plate for 5 to 30 minutes and in an oven for 30 to 90 minutes to form a pattern. A crosslinked film can be obtained.

In addition, "radiation" as used in this invention means containing visible light, an ultraviolet-ray, far ultraviolet rays, X-rays, an electron beam, etc.

Next, the method of forming a color filter protective film using the curable composition of a 2nd aspect of this invention is described.

First, the prepared composition solution is applied to the surface of the substrate on which the cured film is to be formed, and the solvent is removed by preliminary firing to form a coating film of the curable composition.

As mentioned above, as a coating method of a composition solution, it does not specifically limit, For example, various methods, such as a spray method, a roll coat method, and a spin coating method, can be employ | adopted.

Although the conditions of preliminary baking differ also with the kind of each component component, use ratio, etc., Preferably it is 60-120 degreeC and it is about 0.5 to 20 minutes.

In addition, the conditions of the main firing are preferably 150 to 250 ° C. and 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 a combination of two or more steps.

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Synthesis Example 1

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 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 added thereto, followed by nitrogen replacement, followed by gentle stirring. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-1]. Solid content concentration of the obtained polymer solution was 30.8 weight%.

Synthesis Example 2

10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer. 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 added thereto, followed by nitrogen substitution, followed by gentle stirring. The solution temperature was raised to 70 ° C, and the temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-2]. Solid content concentration of the obtained polymer solution was 30.1 weight%.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol ethylmethyl ether were added. 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 tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate were substituted for nitrogen. , Gentle stirring was started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 3 hours to obtain a polymer solution containing a copolymer [A-3]. Solid content concentration of the obtained polymer solution was 30.5 weight%.

<Example 1>

Preparation of Curable Resin Composition

Polymer solution obtained in Synthesis Example 1 (equivalent to 100 parts by weight of a copolymer [A-1] (solid content)) and KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) as component [B] 80 Parts by weight, 10 parts by weight of IRGACURE-819 (Ciba Specialty Chemical Co., Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) as component [C] and γ-glycidoxypropyltri as an adhesion aid 10 parts by weight of methoxy silane and 0.1 parts by weight of SH-28PA (manufactured by Toray Silicone Co., Ltd.) as surfactants were dissolved, mixed and dissolved in diethylene glycol dimethyl ether so that the solid content concentration was 28% by weight. The solution (S-1) of curable resin composition was produced by filtering by the millipore filter of micrometers.

Formation of Planarization Film I

On the glass substrate, the said curable composition (S-1) was apply | coated using the spin coater so that a film thickness might be set to 2 micrometers, and it preliminarily baked on 80 degreeC 3 minutes with the high temperature plate, and formed the coating film. The coating film was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm 2 for 3 seconds using a predetermined pattern mask. This ultraviolet irradiation was performed in air. The main baking of 250 degreeC 1 hour was performed in the clean oven, and the planarization film was formed.

Formation of Planarization Film (II)

On the glass substrate, the board | substrate which has stripe-shaped red, blue, green three color filters (stripe width 100 micrometers) was formed by JSR pigment type color resist (R * G * B). When the surface asperity of the glass substrate which has this color filter was investigated using the surface asperity type alpha-step (made by Tencol Corporation), it was 1.0 micrometer.

On the glass substrate in which this color filter was formed, planarization film II was formed by apply | coating, preliminary baking, and main baking of curable composition similarly to formation of said planarization film I.

Evaluation of Planarization Film

Adhesion

During the adhesion test of JIS K-5400 (1900) 8.5, 100 grid tiles are formed on the flattening film (I) and the flattening film (II) by the cutter knife according to the 8.5 · 2 checker tape method to test the adhesion. Was done. At that time, the number of the peeled checkerboard eyes was shown in Table 1.

The adhesiveness of planarization film I was shown as adhesiveness (I), and the adhesiveness of planarization film II was shown as adhesiveness (II).

Surface hardness

Of the pencil drawing tests of JIS K-5400 (1900) 8.4, the pencil drawing test was performed with respect to the flattening film I formed above according to the test method of 8 * 5 * 1, and the surface hardness of the flattening film was evaluated. It was. The results are shown in Table 1.

Acid resistance

The glass substrate on which the flattening film (I) formed above was formed was immersed for 45 minutes in an aqueous solution of HCl / FeCl ₂ · H ₂ O / water = 2/1/1 weight ratio for 15 minutes, and then the change in the appearance of the flattening film was observed. The acid resistance of a protective film was evaluated by this. At this time, those having no change in appearance were good in acid resistance, and the appearance was peeled off or whitened as poor acid resistance.

Alkali resistance

The glass substrate in which the said protective film (I) was formed was immersed in 5 weight% sodium hydroxide aqueous solution for 30 degreeC for 30 minutes, and the acid resistance of a protective film was evaluated by observing the change of the external appearance of a protective film. At this time, the alkali resistance which the thing did not change in an external appearance and the external appearance peeled off or whitened was made into the alkali resistance defect.

Heat resistance

The protective film formed above was subjected to additional baking at 250 ° C. and 270 ° C. for 60 minutes in a clean oven after measuring the film thickness with a contact film thickness measuring apparatus α-step (manufactured by Tencol Japan Co., Ltd.). After further baking, the film thickness was measured again to calculate the film reduction rate before and after further baking. The results are shown in Table 1.

Heat discoloration resistance

The transmission spectrum in wavelength 400-700 nm was measured about the glass substrate in which the said planarization film I was formed. Subsequently, after heating this glass substrate for 60 minutes at 250 degreeC and 270 degreeC in a clean oven, the transmission spectrum in wavelength 400-700 nm was measured again. Heat discoloration resistance was evaluated by examining changes in the 400 nm transmission spectrum before and after heating. Table 1 shows the rate of change of the transmission spectrum at 400 nm before and after heating.

Flatness

Surface unevenness of the planarization film (II) was measured by the surface uneven system α-step. Table 1 shows the planarization rate calculated according to the following equation.

Planarization rate = Surface unevenness of the flattening film (II) / Surface unevenness of the color filter before coating the protective film × 100 (%)

<Example 2>

In Example 1, the composition solution (S-2) was produced and evaluated in the same manner as in Example 1 except that Alonics TO-1450 was used instead of KAYARAD DPHA as the component (B). The results are shown in Table 1.

<Example 3>

In Example 1, it carried out similarly to Example 1 except having used the solution containing copolymer [A-2] obtained by the synthesis example 2 instead of the solution containing copolymer [A-1], and the composition solution ( S-3) was prepared and evaluated. The results are shown in Table 1.

Comparative Example 1

In Example 1, the composition solution (S) was carried out similarly to Example 1 except having used the solution containing the copolymer [A-3] obtained by the synthesis example 3 instead of the solution containing the copolymer [A-1]. -4) was prepared and evaluated. The results are shown in Table 1.

Adhesion surface
Hardness Acid resistance Alkali resistance Heat resistance Heat discoloration resistance Planarization rate
(%) (I) (II) 250 ℃ 270 ℃ 250 ℃ 270 ℃ Example
One 0/100 0/100 5H Good Good 98 93 3 7 18 Example
2 0/100 0/100 4H Good Good 98 92 3 7 20 Example
3 0/100 0/100 5H Good Good 97 92 3 7 23 Comparative example
One 0/100 0/100 5H Good Good 94 85 5 13 32

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 20 parts by weight of styrene, 65 parts by weight of glycidyl methacrylate and 15 parts by weight of N-phenylmaleimide were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 95 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-4]. Solid content concentration of the obtained polymer solution was 32.8%.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 18 parts by weight of styrene, 62 parts by weight of glycidyl methacrylate and 20 parts by weight of N-cyclohexylmaleimide were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 95 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-5]. Solid content concentration of the obtained polymer solution was 33.0%.

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate and 60 parts by weight of glycidyl methacrylate were added thereto, followed by nitrogen replacement, followed by gentle stirring. The temperature of the solution was raised to 95 ° C, and this temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-6]. Solid content concentration of the obtained polymer solution was 32.8%.

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 6 parts by weight of 2,2'-azobis (isobutyronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were placed. Subsequently, 20 parts by weight of styrene and 80 parts by weight of glycidyl methacrylate were added thereto, followed by nitrogen substitution. The temperature of the solution was raised to 95 ° C., and the temperature was maintained for 4 hours to obtain a polymer solution containing a copolymer [A-7]. Solid content concentration of the obtained polymer solution was 32.4%.

<Example 4>

Preparation of Curable Resin Composition

After diluting the polymer solution (corresponding to 100 parts by weight of the polymer [A-4] (solid content)) containing the polymer [A-4] synthesized in Synthesis Example 4 to 100 parts by weight of propylene glycol monomethyl ether acetate, the components [ D '] 20 parts by weight of epicoat 1032H60 (cyclic aliphatic epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.), 5 parts by weight of γ-glycidoxypropyl diethoxy silane as a silane coupling agent, and Megapack 172 as a surfactant. Fluorine-based surfactant, manufactured by Dai Nippon Ink Chemical Co., Ltd.) 0.02 parts by weight, and 20% by weight of a 25% solution of diethylene glycol methylethyl ether in trimellitic anhydride as a curing agent for component [F] Curable composition (S-5) was obtained by adding a part and stirring sufficiently.

Formation of protective film III

On the glass substrate, the above-mentioned curable composition (S-5) was apply | coated using a spin coater so that a film thickness might be set to 2 micrometers, and it preliminarily baked on 80 degreeC 3 minutes with the high temperature plate, and formed the coating film. . Next, the formed coating film was subjected to the main baking at 250 ° C. for 1 hour in a clean oven to form a protective film.

Formation of color filter protective film IV

On the glass substrate, the board | substrate which has a stripe-shaped red, blue, green three color filter (stripe width 100 micrometers) was formed by JSR pigment type color resist (R * G * B). The surface irregularities of the glass substrate having this color filter were investigated using a surface irregularities-based α-step (manufactured by Tencol Co., Ltd.).

On the glass substrate in which this color filter was formed, the protective film IV was formed by carrying out application | coating, preliminary baking, and main baking of curable composition similarly to formation of the said protective film (III).

Evaluation of the shield

Adhesion

During the adhesion test of JIS K-5400 (1900) 8.5, 100 pieces of checkerboards were formed on the protective film (III) and the protective film (IV) according to the 8.5.2 checker tape method to perform an adhesive test. It was. In that case, the number of the peeled board eyes was shown in Table 2.

Adhesiveness of protective film (III) was shown as adhesiveness (III) and adhesiveness of color filter protective film (IV) as adhesiveness (IV).

Surface hardness

In the pencil drawing test of JIS K-5400 (1900) 8.4, the pencil drawing test was performed about the protective film (III) formed above based on the test method of 8.5 * 1, and the surface hardness evaluation of the protective film was performed. The results are shown in Table 2.

Acid resistance

After immersing the glass substrate on which a protective layer (III) formed by the _{formed, HC1 / FeCl 2 · H 2} O / water = 2/1/45 ℃ during 1 by weight aqueous solution for 15 minutes, by observing the change in appearance of the protective film The acid resistance of a protective film was evaluated. At this time, those having no change in appearance had good acid resistance, and those having peeled or whitened appearance were regarded as poor acid resistance.

Alkali resistance

The glass substrate in which the said protective film (III) was formed was immersed in 5 weight% sodium hydroxide aqueous solution for 30 degreeC for 30 minutes, and the acid resistance evaluation of a protective film was performed by observing the change of the external appearance of a protective film. At this time, the alkali resistance was good, the external appearance peeled off, or the whitened thing was made into the alkali resistance defect that there was no change in an external appearance.

Heat resistance

The protective film (III) formed above was subjected to additional baking at 250 ° C. for 60 minutes and 270 ° C. for 60 minutes in a clean oven after the film thickness was measured by a contact film thickness measuring device α-step (manufactured by Tencol Japan Co., Ltd.). It was. After further baking, the film thickness was again measured to calculate the residual film percentage before and after the additional baking. The results are shown in Table 2.

Heat discoloration resistance

The transmission spectrum in wavelength 400-700 nm was measured about the glass substrate in which the said protective film (III) was formed. Subsequently, after heating this glass substrate for 60 minutes at 250 degreeC and 60 minutes at 270 degreeC in a clean oven, the transmission spectrum in wavelength 400-700 nm was measured again. Heat discoloration resistance was evaluated by examining changes in the 400 nm transmission spectrum before and after heating. Table 2 shows the transmission spectrum values of 400 nm after heating when the transmission spectrum value of 400 nm before heating was 100.

Flatness

Surface irregularities of the color filter protective film IV were measured by the surface irregularities α-step. Table 2 shows the planarization rate calculated according to the following equation.

Planarization rate = Surface unevenness of the color filter protective film (IV) / Surface unevenness of the color filter before the protective film coating × 100 (%)

Example 5

It carried out similarly to Example 4 except having added 1 weight part of 4-acetophenyl dimethylsulfonium hexafluoro antimonate as a component [E '] to the main agent obtained in the said Example 4. The results are shown in Table 2.

<Example 6>

It carried out similarly to Example 4 except having used the polymer of the synthesis example 5 as a component [A ']. The results are shown in Table 2.

<Example 7>

It carried out similarly to Example 5 except having used the polymer of the synthesis example 5 as a component [A ']. The results are shown in Table 2.

<Example 8>

Polymer solution containing polymer [A-4] synthesized in Synthesis Example 4 (corresponding to 100 parts by weight of polymer [A-4] (solid content)) and epicoat 1032H60 (cyclic aliphatic epoxy resin, as component [D '], 20 parts by weight of Yucata Shell Epoxy Co., Ltd., 5 parts by weight of γ-glycidoxypropyldiethoxysilane as a silane coupling agent, and Megapack 172 (a fluorine-based surfactant, manufactured by Dainippon Ink Chemical Co., Ltd.) as a surfactant. ) 0.02 parts by weight was mixed and propylene glycol monomethyl ether acetate was added so as to have a solid concentration of 26% by weight. As a curing agent for component [F], trimellitic anhydride was 25% of diethylene glycol methyl ethyl ether. The curable composition was obtained by adding 20 weight part of solutions in conversion of solid content, and stirring it fully.

Using this curable composition, protective film (III) and protective film (IV) were formed and evaluated similarly to Example 4. The results are shown in Table 2.

Comparative Example 2

It carried out similarly to Example 4 except having used the polymer of the synthesis example 6 as a component [A ']. The results are shown in Table 2.

Comparative Example 3

It carried out similarly to Example 4 except having used the polymer of the synthesis example 7 as a component [A '].

The results are shown in Table 2.

Adhesion surface
Hardness Acid resistance Alkali resistance Heat resistance Heat discoloration resistance Planarization rate
(%) (III) (IV) 250 ℃ 270 ℃ 250 ℃ 270 ℃ Example
4 0/100 0/100 4-5H Good Good 98.8 95.0 98.2 95.5 5.5 Example
5 0/100 0/100 4-5H Good Good 99.0 97.2 98.1 95.1 4.0 Example
6 0/100 0/100 4-5H Good Good 99.1 97.0 98.5 95.8 5.8 Example
7 0/100 0/100 4-5H Good Good 99.4 98.0 98.3 95.0 5.0 Example
8 0/100 0/100 4-5H Good Good 98.8 95.2 98.1 95.6 5.6 Comparative example
2 0/100 0/100 4H Good Good 96.0 73.2 94.9 83.3 4.2 Comparative example
3 0/100 0/100 4-5H Good Good 97.8 87.5 98.3 94.7 4.9

According to the curable composition of this invention, the hardened | cured material excellent in heat resistance, planarization property, and transparency can be manufactured, especially the color filter protective film excellent in heat resistance and transparency.

Claims (7)

[A] a copolymer of (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, (a2) epoxy group-containing monomer, (a3) maleimide monomer and (a4) other monomer, [B] polyfunctional monomers and [C] radical generators Curable composition containing a. The curable composition of Claim 1 which further contains the epoxy resin and [E] acid generator different from [D] the said [A] component. The said (A) component is a (meth) acrylic acid / (meth) acrylic-acid glycidyl / N-phenylmaleimide / styrene copolymer, (meth) acrylic acid / (meth) acrylic acid glycidyl / N- Cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / (meth) acrylic acid glycidyl / N-phenylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) Acrylate copolymer, (meth) acrylic acid / (meth) acrylate glycidyl / N-cyclohexylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate air At least one curable composition selected from the group consisting of coalescing. [A '] copolymer of (a2) epoxy group-containing monomer, (a3) maleimide monomer and (a4) other monomer, [F] at least one compound selected from the group consisting of polyvalent carboxylic anhydrides and polyvalent carboxylic acids, and [D '] An epoxy resin different from the above [A'] component Curable composition containing a. The curable composition of Claim 4 which further contains an [E '] acid generator. The said [A '] component is a (meth) acrylic-acid glycidyl / N-phenylmaleimide / styrene copolymer, (meth) acrylic-acid glycidyl / N-cyclohexyl maleimide / styrene copolymer, Glycidyl (meth) acrylate / N-phenylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate copolymer, glycidyl (meth) acrylate / N -A cyclohexylmaleimide / styrene / tricyclo [5.2.1.O ^2,6 ] decane-8-yl (meth) acrylate copolymer, wherein the curable composition is at least one selected from the group consisting of: The color filter protective film formed from the curable composition in any one of Claims 1-6.