KR20010049485A - A Curable Composition for A Flattened Film and A Flattened Film - Google Patents

Abstract

PURPOSE: To provide a curable composition which can form a highly flat, cured film even on a substrate having a low surface flatness and can form a cured film having a high surface hardness and excellent heat resistance, chemical resistance, etc., by compounding a (co)polymer containing structural units each having a glycidyl group with another epoxy resin and a compound which generates an acid by heat or radiation. CONSTITUTION: This curable composition comprises 100 pts.wt. (co)polymer containing at least 20 mol% structural units represented by formula I (wherein R1 is H or 1-5C alkyl; R2 is H or 1-2C alkyl; and m is 1-8) and having a wt. average mol.wt. of 3,000-300,000, 1-200 pts.wt. epoxy resin other than the (co)polymer, and 0.01-20 pts.wt. compound which generates an acid by heat or radiation, If necessary, the composition may further contain ingredients other than above-described. A solution of the composition is applied to the surface of a substrate, prebaked to remove a solvent to form a coating film, and baked to give a cured film.

Description

A curable composition for a flattening film and a flattening film {A Curable Composition for A Flattened Film and A Flattened Film}

The present invention relates to a curable composition for a flattening film and a flattening film. More specifically, the present invention relates to a curable composition for a flattening film and a flattening film suitable as a material for forming a protective film used for a color filter for a liquid crystal display device (LCD) and a color filter for a charge coupled device (CCD).

Radiation devices such as LCDs and CCDs are immersed in display elements by a solvent, an acid or an alkaline solution, etc. during the manufacturing process, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to high temperature. Therefore, in order to prevent the element from being deteriorated or damaged by such a process, a protective film made of a thin film resistant to such a process is provided.

Such a protective film has high adhesion to the substrate and the lower layer on which the protective film is to be formed, and also the layer formed on the protective film, the film itself is smooth and strong, has transparency, has high heat resistance and light resistance, and is colored for a long time, The performance which does not cause discoloration, whitening, etc., excellent water resistance, solvent resistance, acid resistance, and alkali resistance is calculated | required. As a material for forming a protective film which satisfies such various properties, a thermosetting composition containing a polymer having a glycidyl group disclosed in JP-A-5-78453 is known.

In such a thermosetting composition, a protective film is formed as follows, for example.

First, a thermosetting composition is apply | coated to the surface of the board | substrate which should form a protective film. Subsequently, a protective film is formed by performing preliminary baking (prebaking) of the apply | coated thermosetting composition, and performing main baking (post baking) after that.

On the other hand, in the color liquid crystal display element of a super twisted nematic (STN) system, the uniformity of a cell gap is very important compared with the liquid crystal display element of a twisted nematic (TN) system. Therefore, as a board | substrate used for the STN system color liquid crystal display element, the thing with high flatness of the surface is calculated | required. This is because display unevenness occurs in the obtained liquid crystal display element when a substrate having a low surface flatness is used.

In addition, by adopting a new driving method such as an active addressing method, a display speed higher than that of the conventional STN method can be obtained. As a result, a thinner and more uniform cell gap is required. Very high flatness of the surface is required.

By the way, in the board | substrate with which the color filter was formed, the unevenness | corrugation by a color filter is formed in the surface, for example. And when forming a protective film on the surface in which the color filter was formed using the conventional thermosetting composition, the coating film with high surface flatness can be formed in the application | coating process of a thermosetting composition and a preliminary baking process, but in this baking process, it is comparatively Since it is processed at high temperature, the coating film of a thermosetting composition fluidized, and the coating film surface was deformed according to the unevenness | corrugation by a color filter, and it was difficult to obtain the cured film with high flatness of a surface.

The present invention has been made on the basis of the above circumstances, and the object thereof is to form a cured film having a high flatness on the substrate, even if the substrate has a low surface flatness, and has a high surface hardness, heat resistance, acid resistance, alkali resistance, and the like. It is providing the curable composition for planarizing films which can form the cured film excellent in various tolerances of this, and a planarizing film.

Other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention,

(A) a polymer or copolymer comprising 20 mol% or more of the structural unit represented by the following formula (1) with respect to all repeating units,

(B) epoxy resins other than (A) component, and

(C) It is achieved by the curable composition for planarizing films containing the compound which generate | occur | produces an acid by heat or radiation, and the planarizing film obtained from it.

<Formula 1>

Where

R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and m represents an integer of 1 to 8.

Since the curable composition of this invention contains an epoxy compound and the compound which generate | occur | produces an acid by heat or radiation, it can harden | cure by heating or irradiating a radiation. Therefore, by hardening the surface of a coating film by low-temperature heating or radiation irradiation of the coating film of a curable composition before this baking, it can prevent that a coating film fluidizes in this baking, As a result, a cured film with high flatness of a surface is obtained. Can be formed.

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

The curable composition of the present invention is a polymer or copolymer containing a specific structural unit in a specific ratio (hereinafter referred to as a "specific polymer"). The component (A), the epoxy resin component (B), and the acid by heat or radiation It contains the compound (C) which produces | generates.

<Component (A)>

The specific polymer used as component (A) includes the structural unit represented by the formula (1).

M in Chemical Formula 1 is an integer of 1 to 8, preferably 1 to 4. In addition, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. This alkyl group can be either straight or branched. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl group. In addition, R ² is a hydrogen atom, a methyl group or an ethyl group.

The monomer (hereinafter, referred to as "specific monomer") used to introduce the structural unit represented by the formula (1) is represented by the following formula (2). As a monomer represented by following General formula (2), (meth) acrylic-acid glycidyl, the (alpha)-ethyl acrylate glycidyl, the (alpha)-n-propyl acrylate glycidyl, the (alpha)-n-butyl acrylate glycidyl, (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 can be mentioned. Among these, glycidyl (meth) acrylate is particularly preferable. These monomers can be used individually or in combination of 2 or more types.

Wherein, the definitions of R ¹ , R ^2, and m are the same as in Formula 1,

The specific polymer used as component (A) may be a polymer containing only the structural unit represented by the formula (1). Structural units other than the structural unit represented by the formula (1) may preferably be contained in a proportion of 70 mol% or less, more preferably 5 to 60 mol%, particularly preferably 20 to 50 mol%.

Examples of the monomer for introducing structural units other than the structural units represented by the formula (1) (hereinafter referred to as "other monomers") include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclo (meth) acrylate [5.2.1.O ^2,6 ] decane-8-yl (permissive in the art (Meth) acrylic acid esters such as (meth) acrylic acid dicyclopentanyl), (meth) acrylic acid dicyclopentanyloxyethyl, and (meth) acrylic acid isobonyl; Vinyl aromatic compounds such as styrene, α-methylstyrene, p-methylstyrene, vinylnaphthalene, phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinate Malays such as imidyl-4-maleimidobutylate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimido propionate, N- (9-acryldinyl) maleimide A mid compound can be mentioned. These monomers can be used individually or in combination of 2 or more types.

The molecular weight of the specific polymer used as the component (A) is not particularly limited as long as it can form a coating film having a flat surface by applying a solution of the curable composition obtained, the thickness of the coating film to be formed, the solution coating conditions of the curable composition, Although it selects suitably according to the objective etc., it is preferable that the polystyrene reduced weight average molecular weight is normally in the range of 3,000-300,000, and it is more preferable to exist in the range of 3,000-100,000.

In addition, when using the specific polymer which has a structural unit represented by General formula (1) and structural units other than these as component (A), this polymer may be one of a random copolymer and a block copolymer of a specific monomer and another monomer. have. Random copolymers are more preferred.

<Component (B)>

As epoxy resins other than a component (A), a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, and a cresol novolak-type epoxy resin can be used, for example. These can be obtained as a commercial item. For example, as bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above, Yuka Shell Epoxy Co., Ltd. make), and as bisphenol F type epoxy resin, Epicoat 807, 834 (Above, Yuka Shell Epoxy Co., Ltd.), Epiphenol 152, 154, 157H65 (above, Yuka Shell Epoxy Co., Ltd.), EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.) ), Cresol novolac type epoxy resin, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 ( Yuka Shell Epoxy Co., Ltd.), CY175, CY177, CY179 (above, manufactured by CIBA-GEIGY AG), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (above, UCC) Company), Shodine 509 (Showa Denko Co., Ltd.), Araldite CY-182, CY-192, CY-184 (above, manufactured by CIBA-GEIGY AG), epicron 200, 400 (more, die Nippon Ink Kogyo Co., Ltd.) Epicoat 871, 872, EP1032H60 (above, manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5662 (above, manufactured by Celanese Co., Ltd.), epicoat 190P, 191P as aliphatic polyglycidyl ether (As above, Yuka Shell Epoxy Co., Ltd.), epolite 100MF (Kyoesha Yushi Chemical Industries, Ltd. make), and Epiol TMP (made by Nippon Yushi Co., Ltd.) are mentioned.

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 an epoxy resin (B) per 100 weight part of (A) component becomes like this. Preferably it is 1-200 weight part, More preferably, it is 3-100 weight part.

In addition, although said (A) component can also be called an epoxy resin, the epoxy resin of the said (B) component is a low molecular weight compared with (A) component, and differs in the point which is effective in the improvement of planarization property.

<Component (C)>

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, for example. Especially, a sulfonium salt and a benzothiazonium salt are preferable.

Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium Hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4 Alkylsulfonium salts such as acetoxyphenylsulfonium 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 hexafluoroarsenate, 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 hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5- dibenzylsulfonium salts such as tert-butylphenylsulfonium hexafluoroantimonate, 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, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; And sulfonium salts represented by the following (1) to (7).

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzylbenzo such as benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate A thiazonium salt is mentioned.

Among them, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate , Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate and the like are preferably used. do. As these commercial items, San-Aid SI-60L, SI-80L, SI-100L, SI-L85, SI-Ll10, SI-L145, SI-L147, SI-L150, SI-L160 (Sanshin Kagaku Kogyo Co., Ltd.) Production).

The compound which generates an acid by such heat can also function as a compound which generates 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, trichloromethyl-s-triazines, diaryl iodonium salts, and triarylsulfonium salts can be used, for example.

Examples of the trichloromethyl-s-triazines include tris (2,4,6-trichloromethyl) -s-triazine and 2-phenyl-bis (4,6-trichloromethyl) -s-tri Azine, 2- (4-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-tri Azine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s- Triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl)- s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) -bis (4,6-trichloromethyl ) -s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6- Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2- Methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine , 2- (3-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxy-β-styryl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4 -Methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloro Methyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran -2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -bis (4,6 -Trichloromethyl) -s-triazine is mentioned.

Examples of the diaryl iodonium salts include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, and diphenyl iodonium trifluoromethane. Sulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodinium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate , 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl Iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluoroarsenate, bis (4-t ert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate have.

Examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethane. Sulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosph Phonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4 -Methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldiphenyl Hexafluoroarsenate, 4-phenylthiophenyldiphenyl trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl trifluoroacetate, and 4-phenylthiophenyldiphenyl-p-toluenesulfonate. .

Among these compounds, as trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β -Styryl) -bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan -2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6- Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4 -Methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate or 4-methoxyphenylphenyl iodonium Trifluoroacetate;

Examples of the triarylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenyl trifluoromethanesulfonate, or 4-phenylthiophenyldiphenyl trifluoroacetate is mentioned as a preferable thing, respectively.

The use ratio of the compound (C) 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 (C) component is less than 0.01 weight part with respect to 100 weight part of (A) components, since the amount of acid which generate | occur | produces by receiving heating or radiation is small, the crosslinking of (A) component and (B) component is sufficient. It does not advance 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 the use ratio of (C) component exceeds 20 weight part with respect to 100 weight part of (A) component, film | membrane roughness tends to arise in a coating film.

<Other ingredients>

In addition to the component (A), component (B), and component (C) mentioned above, the curable composition of this invention contains a silane coupling agent, a hardening adjuvant, a hardening accelerator, surfactant, and a ultraviolet absorber as needed, as other components. Can be.

[Silane coupling agent]

The silane coupling agent is used to improve the adhesion between the cured film and the substrate on which the cured film should be formed, and is a functional group-containing alkoxy silane having reactive substituents (functional groups) such as carboxyl groups, methacryloyl groups, isocyanate groups and epoxy groups. Compounds are used.

Examples of such functional group-containing alkoxy silane compounds include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ. -Glycidoxy propyl trimethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, and (gamma)-glycidoxy propyl diethoxysilane are mentioned. These can be used individually or in combination of 2 or more types.

The use ratio of the silane coupling agent is preferably 100 parts by weight or less, more preferably 0.1 to 100 parts by weight, particularly preferably 1 to 40 parts by weight, based on 100 parts by weight of component (A). When the use ratio of a silane coupling agent is less than 0.1, the effect of providing sufficient adhesiveness between a cured film and the board | substrate which should form a cured film 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 Supplements]

The curing aid acts as a curing agent for the particular polymer and epoxy resin (B) used as component (A). These curing agents are used auxiliary when crosslinking is insufficient only by curing with a compound that generates an acid by heat or radiation of component (C). As such a hardening adjuvant, polyhydric carboxylic anhydride or polyhydric carboxylic acid can be used suitably.

As a specific example of polyhydric carboxylic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride Aliphatic dicarboxylic anhydrides such as acids; Alicyclic polyvalent carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; Aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenonetetracarboxylic anhydride; Ester group-containing acid anhydrides such as ethylene glycol bis anhydrous trimellitate and glycerin tris anhydrous trimellitate. Among these, aromatic polyhydric carboxylic anhydride, especially trimellitic anhydride, is preferable in that a cured film having high heat resistance can be 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; Alicyclic polyhydric carboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 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. Among these, aromatic polyhydric carboxylic acid is suitable from the viewpoint of the reactivity of the curable composition, the heat resistance of the cured film formed, and the like.

These polyhydric carboxylic anhydrides or polyhydric carboxylic acids can be used individually or in combination of 2 or more types.

The use ratio of a hardening adjuvant becomes like this. Preferably it is 1-40 weight part with respect to 100 weight part of component (A), More preferably, it is 5-20 weight part.

[Hardening accelerator]

The hardening accelerator is used to accelerate the reaction between the component (A) and the component (B) and the curing aid, that is, the curing agent. Generally, a compound having a heterocyclic structure containing a secondary nitrogen atom or a tertiary nitrogen atom is used. Used.

Specific examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, indole, indazole, benzimidazole or isocyanuric acid or derivatives thereof. Among them, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-ethyl-4-methyl-1- (2'-cyanoethyl) imidazole, 2-ethyl-4-methyl-1- [2 '-(3 ", 5" -diaminotriazinyl) ethyl] imi Preferred are imidazole derivatives such as dazole and benzimidazole, most preferably 2-ethyl-4-methylimidazole, 4-methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole This is used.

These compounds can be used individually or in combination of 2 or more types as a hardening accelerator.

A hardening accelerator is used in the ratio of preferably 0.01-10 weight part, More preferably, 0.05-5 weight part with respect to 100 weight part of component (A).

[Surfactants]

As surfactant, a fluorochemical surfactant and silicone type surfactant can be used suitably.

As the fluorine-based surfactant, preferably, a compound having a fluoroalkyl or a fluoroalkylene group in at least one portion of the terminal, main chain and side chain can be used. Specific examples thereof include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether and octaethylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycoldi (1,1,2 , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2, 8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoroalkyloxyethylene ether, diglycerin Tetrakis, fluoroalkyl ammonium azide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and fluorine alkyl ester. Moreover, as these commercial items, BM-1000, BM-1100 (above, BM Chemie company make), Megafax F142D, F172, F173, F183, F178, F191, F471 (above, Dai Nippon Ink Chemical Industries, Ltd. make) ), Fluoride FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd. product) is mentioned.

As the silicone-based surfactant, for example, tresilicon DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, FS-1265-300 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300 And those marketed under the trade names of TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, Toshiba Silicone Co., Ltd.).

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

Although the use ratio of surfactant differs also with the kind and ratio of each component which comprises the kind and curable composition, Preferably it is 0-10 weight part with respect to 100 weight part of component (A), More preferably, it is 0.0001-5 Used in the range of parts by weight.

The curable composition of the present invention is prepared by uniformly mixing the above-mentioned component (A), component (B), component (C) and other components contained as necessary, and usually, each component is dissolved in an organic solvent to form a solution of the composition. It is prepared as.

As an organic solvent used in order to prepare this composition solution, if a component can be melt | dissolved uniformly and does not react with each component at the same time, it will not specifically limit. Generally, it is easy to form a coating film, For example, glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and ethylene glycol monobutyl ether acetate; Diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetic acid, methyl 2-hydroxy-3-methylbutanoic acid, methyl 3-methoxypropionate, 3-meth Ester, such as ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butyl acetate, methyl lactate, and ethyl lactate, can be used. These solvents can be used alone or in combination of two or more thereof.

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

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

That is, the prepared composition solution is applied to the surface of the substrate on which the cured film should be formed and prebaked to remove the solvent to form a coating film of the curable composition, or the surface of the coating film is further irradiated with radiation to the coating film after preliminary firing. After hardening, the cured film is formed by performing main baking.

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

Although the conditions of preliminary baking differ also with kinds, usage ratios, etc. of each component of a composition solution, Preferably it is about 0.5 to 20 minutes at 60-120 degreeC.

Moreover, the conditions of this baking are preferably about 0.2 to 2.0 hours at 150-250 degreeC.

In addition, each preliminary baking and this baking can be performed in one step or in combination of 2 or more steps.

Since the curable composition of this invention contains an epoxy compound as a component (A) and (B) and a compound which generate | occur | produces an acid by heat or radiation as a component (C), hardening the surface by heating or irradiation of a coating film. You can. Therefore, after precuring by apply | coating a curable composition or forming the coating film of a curable composition, by irradiating this coating film with radiation and hardening the surface of a coating film, the surface of a coating film is prevented from flowing in this baking, As a result, a cured film with high surface flatness can be formed.

Moreover, the cured film formed by the curable composition of this invention is excellent in various physical properties, as is clear from the following example, For example, it is very preferable as a protective film used for the color filter for LCD and the color filter for CCD.

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In the examples, "%" means "% by weight" unless otherwise specified.

<Synthesis example 1> (synthesis of polymer (A1))

80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added to 200 parts by weight of propylene glycol monomethyl ether acetate, and mixed with 4.0 parts by weight of azobisisobutyronitrile (AIBN), followed by polymerization at 95 ° C for 3 hours. To obtain a polymer solution having a polymer (A1) concentration of 32%.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A1) was 4,000.

Synthesis Example 2 (Synthesis of Polymer (A2))

50 parts by weight of glycidyl methacrylate and 50 parts by weight of dicyclopentanyl methacrylate were added and mixed to 200 parts by weight of propylene glycol monomethyl ether acetate, and 4.0 parts by weight of azobisisobutyronitrile (AIBN) was added thereto. Polymerization was carried out at 3C for 3 hours to obtain a polymer solution having a polymer (A2) concentration of 32%.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A2) was 5,000.

Synthesis Example 3 (Synthesis of Polymer (A3))

60 parts by weight of glycidyl methacrylate, 30 parts by weight of styrene and 10 parts by weight of methyl methacrylate were added and mixed to 200 parts by weight of propylene glycol monomethyl ether acetate, and 4.0 parts by weight of azobisisobutyronitrile (AIBN) was added. Thereafter, polymerization was carried out at 95 ° C for 3 hours to obtain a polymer solution having a polymer (A3) concentration of 32%.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer (A3) was 4,000.

<Example 1>

Preparation of Curable Compositions

After diluting the polymer solution (corresponding to 100 parts by weight of the polymer (A1) (solid content)) containing the polymer (A1) synthesized in Synthesis Example 1 to 100 parts by weight of propylene glycol monomethyl ether acetate, it was epi as component (B). 20 parts by weight of coat 828 (bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.), 2 parts by weight of 4-acetophenyldimethylsulfonium hexafluoroantimonate as component (C), and? -Gly as a silane coupling agent. 6 parts by weight of cydoxypropyl diethoxysilane, 0.1 parts by weight of 2-ethyl-4-methylimidazole as a curing accelerator, and Megafax F172 as a surfactant (fluorine-based surfactant, manufactured by Dainippon Ink & Chemicals Co., Ltd.) 0.01 Curable composition (S1) was obtained by adding a weight part and fully stirring.

Formation of Planarization Film I

The above-mentioned curable composition (S1) was apply | coated on a glass substrate using a spin coater so that a film thickness might be set to 2 micrometers, and it preliminarily baked on 80 degreeC and the conditions of 3 minutes with a hot plate, and formed the coating film. Subsequently, the formed coating film was subjected to the main baking at 250 ° C. for 1 hour in a clean oven to form a flattening film.

Formation of Planarization Film (II)

On the glass substrate, the board | substrate which has a stripe-like red, blue, green three-color 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 examined using a surface irregularities-based α-step (manufactured by Tencol Corporation).

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

In the adhesion test of JIS K-5400 (1900) 8.5, according to the 8.5 · 2 checker tape method, 100 checkerboards were formed on the flattening film (I) and the flattening film (II) with a cutter knife to test the adhesion. Was performed. In this case, Table 1 shows the number of the tiles remaining without peeling.

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

Of the pencil scratch tests of JIS K-5400 (1900) 8.4, the pencil scratch test was performed about the planarization film I formed above based on the test method of 8.5 * 1, and the surface hardness evaluation of the planarization film was performed. The results are shown in Table 1.

Acid resistance

The glass substrate on which the flattening film (I) formed above was formed was immersed at 45 ° C. for 15 minutes in an aqueous solution of HC1 / FeCl ₂ · H ₂ O / water = 2/1/1 weight ratio, and then observed the appearance change of the flattening film. The acid resistance of the protective film was evaluated. At this time, the acid resistance was good (0) and the thing which peeled or whitened the thing which did not change in external appearance was made into acid resistance defect (x).

Alkali resistance

The glass substrate on which the flattening film (I) was formed was immersed in a 5% by weight aqueous sodium hydroxide solution at 30 ° C. for 30 minutes, and then the acid resistance of the protective film was evaluated by observing the appearance change of the flattening film. At this time, the alkali resistance good (0) and the external appearance peeled or whitened that the thing did not change in external appearance were made into alkali resistance defect (x).

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 in the clean oven, the transmission spectrum in wavelength 400-700 nm was measured again. The change in the 400 nm transmission spectrum before and after the heating was examined and heat discoloration resistance was evaluated. The rate of change of the transmission spectrum of 400 nm before and after heating is shown in Table 1.

Flatness

The surface unevenness of the planarization film II was measured by the surface unevenness α-step. Table 1 shows the planarization rate calculated according to the following equation.

Surface unevenness of the flattening ratio = surface unevenness of the flattening film (II) / color filter before coating the protective film × 100

<Example 2>

In Example 1, the curable composition (S2) was obtained in the same manner as in Example 1 except that the addition amount of the epicoat 828 as the component (B) was 40 parts by weight.

In addition, in Example 1, except having used the said curable composition (S2) instead of curable composition (S1), it carried out similarly to Example 1, and formed and evaluated the planarization film (I) and the planarization film (II). The results are shown in Table 1.

<Example 3>

In Example 1, the curable composition (S3) was obtained in the same manner as in Example 1 except that Epicoat 152 was used instead of Epicoat 828 as the component (B).

In addition, in Example 1, except having used the said curable composition (S3) instead of curable composition (S1), it carried out similarly to Example 1, and formed and evaluated the planarization film (I) and the planarization film (II). The results are shown in Table 1.

<Example 4>

Preparation of Curable Compositions

In Example 1, a solution containing the polymer (A2) synthesized in Synthesis Example 2 was used instead of the solution containing the polymer (A1) and 4-acetoxyphenyldimethylsulfonium hexafluoro as component (C). Curable composition (S4) was obtained like Example 1 except having used 2 weight part of antimonates.

Formation of Planarization Film I

The said curable composition (S4) was apply | coated on the glass substrate using a spin coater so that a film thickness might be set to 2 micrometers, and the preliminary baking was performed on 80 degreeC and the conditions of 3 minutes with a hot plate, and the coating film was formed. Subsequently, 200 mJ / cm in terms of i-line was converted into ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) using an exposure machine Canon PLA50lF (manufactured by Canon Corporation) to the formed coating film. ^It irradiated with the exposure amount of ² . Thereafter, the substrate on which the coating film was formed was subjected to main baking at 250 ° C. for 1 hour in a clean oven to form a flattening film.

Formation of Planarization Film (II)

On the glass substrate, the color filter which has a stripe-like red, blue, and green three color layer (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 colored layer was investigated using the surface asperity type alpha-step (made by Tencol Corporation), it was 1.0 micrometer.

On the glass substrate with this colored layer formed, planarization film (II) was formed by apply | coating, preliminary baking, light irradiation, and main baking of curable composition similarly to formation of said planarization film (I).

Evaluation of Planarization Film

The flattening film was evaluated similarly to Example 1 using planarization film I and planarization film II formed above. The evaluation results are shown in Table 1.

<Example 5>

In Example 1, a solution containing the polymer (A3) synthesized in Synthesis Example 3 was used instead of the solution containing the polymer (A1), and 3-benzylbenzothiazonium hexafluoroantimo as component (C). Curable composition (S5) was obtained like Example 1 except having used 2 weight part of nates.

In addition, in Example 1, planarizing film (I) and planarizing film (II) were formed and evaluated similarly to Example 1 except having used the said curable composition (S5) instead of curable composition (S1). The results are shown in Table 1.

<Example 6>

20 weight part of trimellitic anhydride was melt | dissolved in diglyme (diethylene glycol dimethyl ether), and the hardening | curing agent solution containing the diglyme solution of trimellitic anhydride of 30 weight% of concentration was prepared.

The said hardening | curing agent solution was added and mixed with the curable composition (S2) prepared in the said Example 2, and the curable composition (S6) was prepared.

In addition, in Example 1, except having used the said curable composition (S6) instead of curable composition (S1), it carried out similarly to Example 1, and formed and evaluated the planarization film (I) and the planarization film (II). The results are shown in Table 1.

<Comparative Example>

In Example 1, the curable composition (R1) was prepared in the same manner as in Example 1 except that (C) component was not added.

In addition, in Example 1, except having used the said curable composition (R1) instead of curable composition (S1), it carried out similarly to Example 1, and formed and evaluated the planarization film (I) and the planarization film (II). The results are shown in Table 1.

According to the curable composition of this invention, even if it is a board | substrate with a low surface flatness as mentioned above, the cured film with high flatness can be formed on the board | substrate, and its surface hardness is high, and it is excellent in various resistances, such as heat resistance, acid resistance, and alkali resistance A cured film can be formed.

Claims (5)

(A) a polymer or copolymer comprising 20 mol% or more of the structural unit represented by the following formula (1) with respect to all repeating units, (B) epoxy resins other than (A) component, and (C) Curable composition for planarizing films containing compounds which generate | occur | produce an acid by heat or radiation. <Formula 1> Where R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, m represents the integer of 1-8. The composition of Claim 1 whose epoxy resin (B) other than (A) component is a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, or a cresol novolak-type epoxy resin. The composition according to claim 1, wherein the compound which generates an acid by heat or radiation is at least one onium salt selected from the group consisting of sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts. The method according to claim 1, wherein 100 parts by weight of the polymer or copolymer (A), 1 to 200 parts by weight of the epoxy resin (B) other than (A) and 0.01 to 20 parts by weight of the compound (C) which generates an acid by heat or radiation A composition comprising a part. The flattening film obtained from the curable composition for flattening films of Claim 1.