JP2000119472A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide thermosetting resin compositions suitable as materials for forming which meet various properties to be traditionally required as protective optical device protective film films, specifically adhesion, surface hardness, transparency, heat resistance, light-resistance, chemical resistance, water resistance and the like and can flatten the difference in the steps of color filters. SOLUTION: Thermosetting resin compositions comprise [A] a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride, (a2) an epoxy group-containing unsaturated compound, and (a3) an olefinic unsaturated compound other than said (a1) and (a2), [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a compound which generates a radical by heat.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermosetting resin composition. More specifically, the present invention relates to a thermosetting resin composition suitable for use as a protective film forming material for optical devices, particularly for color filters.

[0002]

2. Description of the Related Art Optical devices such as liquid crystal display devices and solid-state imaging devices are immersed in, for example, a solvent, an acid, or an alkaline solution during a manufacturing process, or are sputtered when a wiring electrode layer is formed. They may be subjected to severe processing such as local high-temperature heating. For this reason, these elements may be provided with a protective film on the surface in order to prevent deterioration during manufacturing.

[0003] The protective film is required to have various properties that can withstand the above-mentioned treatments. Specifically, the protective film must have excellent adhesion to a substrate or a lower layer, be smooth and have a high surface hardness, and be transparent. It has excellent heat resistance and light resistance so that there is no deterioration such as coloring, yellowing, whitening, etc. over a long period of time, chemical resistance such as solvent resistance, acid resistance, alkali resistance, etc. Excellent water resistance is required.

On the other hand, when such a protective film is applied to a color filter of a color liquid crystal display element, it is generally desired that the step of the color filter as a base substrate can be flattened. In particular, when manufacturing an STN-type color liquid crystal display device, the precision of bonding between the color filter and the opposing substrate must be very strictly performed, and it is essential to make the cell gap between the substrates uniform. Has become.

Therefore, a material that satisfies the above-described various characteristics required for the protective film and that can flatten the steps on the surface of the color filter as the underlying substrate has been desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide various properties conventionally required as a protective film, specifically, adhesion, surface hardness, transparency, heat resistance, light resistance, chemical resistance, and the like. An object of the present invention is to provide a thermosetting resin composition suitable as a material for forming a protective film for an optical device, which satisfies water resistance and the like and can flatten a step of a color filter as a base substrate. Other objects and advantages of the present invention will become apparent from the following description.

[0007]

According to the present invention, the above objects and advantages of the present invention are as follows: [A] (a1) Unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter referred to as "a").
Also referred to as “compound (a1)”. ), (A2) an epoxy group-containing unsaturated compound (hereinafter, also referred to as “compound (a2)”), (a3) an olefinically unsaturated compound other than the above (a1) and (a2) (hereinafter, “compound (a3) ) "), [B] a polymerizable compound having an ethylenically unsaturated bond (hereinafter, also referred to as" polymerizable compound [B] "), and [C] radicals generated by heat. This is achieved by a thermosetting resin composition characterized by containing a compound (hereinafter, also referred to as “thermal radical polymerization initiator [C]”). Hereinafter, the thermosetting resin composition of the present invention will be described in detail.

Copolymer [A] Copolymer [A] is composed of compound (a1), compound (a2) and compound (a3). For example, these compounds are prepared in a solvent in the presence of a polymerization initiator. It can be synthesized by radical polymerization.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a1), preferably 5 units.
-40% by weight, particularly preferably 10-30% by weight. Copolymers containing less than 5% by weight of the structural unit tend to have reduced heat resistance, chemical resistance and surface hardness, while copolymers containing more than 40% by weight have reduced storage stability. As the compound (a1), for example, acrylic acid,
Monocarboxylic acids such as methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; and anhydrides of these dicarboxylic acids. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity, heat resistance and easy availability. These compounds (a1) are used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a2), preferably 1
The content is 0 to 70% by weight, particularly preferably 20 to 60% by weight. When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the obtained protective film tend to decrease,
On the other hand, if it exceeds 70% by weight, the storage stability of the copolymer tends to decrease.

As the compound (a2), for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4 -Epoxybutyl, methacrylic acid-3,4-
Epoxy butyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate,
O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferably used from the viewpoint of increasing the copolymerization reactivity and the heat resistance and hardness of the resulting protective film. These compounds (a2) are used alone or in combination.

The copolymer [A] used in the present invention comprises a structural unit derived from the compound (a3), preferably 1
The content is 0 to 70% by weight, particularly preferably 20 to 50% by weight. When this constituent unit is less than 10% by weight, the storage stability of the copolymer [A] tends to decrease, while when it exceeds 70% by weight, the heat resistance and the surface hardness of the copolymer [A] become poor. descend.

The compound (a3) includes, for example, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; alkyl acrylates such as methyl acrylate and isopropyl acrylate; Cyclic alkyl methacrylates such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyloxyethyl methacrylate, and isobornyl methacrylate;
Acrylic cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentaoxyethyl acrylate, and isobornyl acrylate;
Aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; aryl acrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 2-hydroxyethyl methacrylate, 2-hydroxy Hydroxyalkyl esters such as propyl methacrylate;
And styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3- Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-
Methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. These compounds (a3) are used alone or in combination.

As described above, the copolymer [A] used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be heated without using a special curing agent. Can be easily cured.

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

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

Polymerizable Compound [B] As the polymerizable compound [B] used in the present invention, a monofunctional, difunctional or trifunctional or more (meth) acrylate having good polymerizability and a protective film to be obtained is obtained. From the viewpoint of improving heat resistance and surface hardness.

As the monofunctional (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylate Acryloyloxyethyl-
2-hydroxypropyl phthalate and the like can be mentioned.
Commercially available products include, for example, Aronix M-101,
M-111, M-114 (Toa Gosei Chemical Industry Co., Ltd.)
KAYARAD TC-110S, TC-12
OS (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 158, 23
11 (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the above bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate,
Examples thereof include polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and bisphenoxyethanol full orange acrylate. Examples of commercially available products include Aronix M-210, M-240, M-6200 (manufactured by Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, and H
X-220, R-604 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the above trifunctional or higher-functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. As commercially available products, for example, Aronix M-309, M-400, and M-40
2, M-405, M-450, M-7100, M-8030, M-8060 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, DPH
A, DPCA-20, DPCA-30, DPCA
-60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), VISCOAT 295, 300, 360, GPT, 3
PA and 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.). These monofunctional, difunctional or trifunctional or higher (meth) acrylates are used alone or in combination.

Thermal radical polymerization initiator [C] Examples of the thermal radical polymerization initiator [C] used in the present invention include 2,2'-azobisisobutyronitrile,
2'-azobis-2-methylbutyronitrile, 2,2 '
-Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis-1-cyclohexylnitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis- 4-cyanovaleric acid, 1,
Azo compounds such as 1'-azobis (1-acetoxy-1-phenylethane); organic compounds such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, and 1,1'-bis (tert-butylperoxy) cyclohexane Peroxides can be mentioned.

Thermosetting Resin Composition The thermosetting resin composition of the present invention comprises the above-mentioned copolymer [A], polymerizable compound [B] and thermal radical polymerization initiator [C] uniformly. It is prepared by mixing. Usually, the thermosetting resin composition of the present invention is used in the form of a solution after being dissolved in an appropriate solvent. For example, a thermosetting resin composition in a solution state is prepared by mixing a copolymer [A], a polymerizable compound [B], a thermal radical polymerization initiator [C], and other compounding agents at a predetermined ratio. can do.

The thermosetting resin composition of the present invention comprises a polymerizable compound [B], based on 100 parts by weight of the copolymer [A].
Preferably from 20 to 250 parts by weight, more preferably from 50 to 250 parts by weight.
It is contained at a rate of 150 parts by weight. When the amount of the polymerizable compound [B] is less than 20 parts by weight, the obtained protective film cannot be sufficiently flattened. When the amount exceeds 250 parts by weight, the adhesion of the obtained protective film tends to decrease.

The thermosetting resin composition of the present invention comprises a thermal radical initiator [C] based on 100 parts by weight of the copolymer [A].
Is preferably 1 to 20 parts by weight, more preferably 3 to 1 part by weight.
It is contained in a proportion of 5 parts by weight. When the amount of the polymerizable compound [C] is less than 1 part by weight, the heat resistance and flatness of the obtained protective film are liable to decrease, and when the amount exceeds 20 parts by weight, the coating film tends to be rough.

As a solvent used for preparing the thermosetting resin composition of the present invention, the components of the copolymer [A], the polymerizable compound [B] and the thermal radical polymerization initiator [C] are uniformly dissolved. Those which can be formed and do not react with each component are used.

Specifically, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol such as methyl cellosolve acetate and ethyl cellosolve acetate Alkyl ether acetates; diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl Propylene glycol alkyl ether propionates such as ether propionate and propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone;
Ketones such as hydroxy-4-methyl-2-pentanone and methyl isoamyl ketone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2 -Ethyl hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate,
Propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, methoxyacetic acid Ethyl, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate,
Ethoxy butyl acetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate,
Propyl butoxyacetate, butyl butoxyacetate, 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 -Ethyl methoxypropionate,
Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3
-Ethyl ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-
Methyl propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate,
Butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3
Esters such as propyl butoxypropionate and butyl 3-butoxypropionate.

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

Further, a high boiling point solvent may be used in combination with the above-mentioned solvent. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol,
1-nonanol, benzyl alcohol, benzyl acetate,
Examples include ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0030] The thermosetting resin composition of the present invention may contain other components in addition to the above components, if necessary, as long as the object of the present invention is not impaired.

Here, as another component, a surfactant for improving coatability can be mentioned. Commercially available products include, for example, BM-1000, BM-1100
(Manufactured by BMCHEMIE), Megafac F142D,
F172, F173, F183 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-135, FC-1
70C, FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, S-113,
S-131, S-141, S-145, S-3
82, SC-101, SC-102, SC-10
3, SC-104, SC-105, SC-106
(Manufactured by Asahi Glass Co., Ltd.), F-top EF301, 303,
352 (manufactured by Shin-Akita Chemical Co., Ltd.), SH-28PA, S
H-190, SH-193, SZ-6032, SF-8
428, DC-57, and DC-190 (manufactured by Toray Silicone Co., Ltd.).

In addition, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; Nonionic surfactants such as ethylene aryl ethers, polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.)
Co., Ltd.), (meth) acrylic acid copolymer polyflow No.
57, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

These surfactants are copolymers [A] 1
It is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 00 parts by weight. When the amount of the surfactant is more than 5 parts by weight, the film tends to be rough at the time of coating.

In order to improve the adhesion to the substrate, an adhesion aid may be used. As such an adhesion aid, a functional silane coupling agent is preferably used, and for example, a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferably used. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.

[0035] Such an adhesion promoter is a copolymer [A] 1
It is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less based on 00 parts by weight. When the amount of the adhesion aid exceeds 20 parts by weight, heat resistance tends to decrease. Furthermore, an epoxy resin can be mixed and used for the purpose of increasing the adhesion.

As the epoxy resin, for example, Epicoat 1001, 1002, 1003, 1004, 1
007, 1009, 1010, 828 (trade names;
Bisphenol A such as Yuka Shell Epoxy Co., Ltd.)
Bisphenol F type epoxy resins such as Epicoat 807 (trade name; Yuka Shell Epoxy Co., Ltd.); Epicoat 152 and Epi154 (trade name; Yuka Shell Epoxy Co., Ltd.), EPPN201, 202
Phenol novolak type epoxy resin such as (trade name; manufactured by Nippon Kayaku Co., Ltd.); EOCN102, 103S, 104S, 1020, 1025, 1027 (trade name; manufactured by Nippon Kayaku Co., Ltd.); Name;
Cresol novolak type epoxy resin such as Yuka Shell Epoxy Co., Ltd .; Epicoat 1032H60, X
Y-4000 (trade name; Yuka Shell Epoxy Co., Ltd.)
Such as polyphenol type epoxy resin, CY-175,
177, 179, Araldite CY-182, 1
92, 184 (trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, 4299, 42
21, 4206 (trade name; manufactured by UCC), Shodyne 509 (trade name, manufactured by Showa Denko KK), Epicron 2
00, 400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, and 5662 (trade name;
Cycloaliphatic epoxy resins such as Celanese Coatings Co., Ltd .; Epolite 100MF (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Epiol TMP (Nippon Yushi Co., Ltd.)
And aliphatic polyglycidyl ethers.

Such an epoxy resin is preferably used in an amount of 20 parts by weight or less based on 100 parts by weight of the copolymer [A]. When the amount of the epoxy resin exceeds 20 parts by weight, the hardness tends to decrease.

The composition solution prepared as described above can be used after being filtered using a millipore filter having a pore size of about 0.2 to 0.5 μm.

Formation of Protective Film The thermosetting resin composition of the present invention can be formed into a coating film by applying it to the surface of an underlying substrate and removing the solvent by pre-baking. As a coating method, various methods such as a spray method, a roll coating method, and a spin coating method can be adopted.

The prebaking conditions vary depending on the type of each component, the mixing ratio, and the like.
C. for about 1 to 15 minutes. Next, the prebaked coating film is heated by a heating device such as a hot plate or oven.
A target protective film can be obtained by performing a heat treatment at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven.

[0041]

EXAMPLES The present invention will be described more specifically with reference to the following synthesis examples and examples, but the present invention is not limited to the following examples. Evaluation of various characteristics was performed by the following methods.

Evaluation of Transparency Spectrophotometer (150-20 type double beam (Hitachi, Ltd.)
The transmittance at 400 to 800 nm was measured using the following method. At this time, the case where the minimum transmittance exceeded 95% was [○], the case where it was 90 to 95% was [△], and the case where it was less than 90% was [x].

Evaluation of Heat Resistance The substrate on which the coating film was formed was heated in an oven at 250 ° C. for one hour, and the heat resistance was evaluated by measuring the film thickness before and after heating. When the residual film ratio exceeds 95%, [○]
The case of 90 to 95% was evaluated as [△], and the case of less than 90% was evaluated as [x].

Evaluation of Heat Discoloration Resistance The measurement substrate was heated in an oven at 250 ° C. for 1 hour, and the heat resistance was evaluated by a change in transmittance before and after heating. At this time, the case where the change rate was less than 5% was [o], the case where it was 5 to 10% was [△], and the case where it exceeded 10% was [x].
The transmittance was determined in the same manner as in the evaluation of transparency.

Measurement of Surface Hardness The surface hardness was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990.

Evaluation of Flatness The level difference of the substrate was measured using a stylus type film thickness measuring device.

Evaluation of adhesiveness Pressure cooker test (120 ° C., 100% humidity,
After 4 hours), it was evaluated by a cross cut tape peeling test. The evaluation result was represented by the number of remaining crosscuts in 100 crosscuts.

Synthesis Example 1 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were charged into a flask equipped with a condenser and a stirrer. Subsequently, 25 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentanyl methacrylate were charged and replaced with nitrogen, and then gentle stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-1]. The solid content concentration of the obtained polymer solution was 33.0% by weight.

Synthesis Example 2 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were charged into a flask equipped with a condenser and a stirrer. Then 5 parts by weight of styrene and 1 part of methacrylic acid
After 6 parts by weight, 40 parts by weight of glycidyl methacrylate and 34 parts by weight of dicyclopentanyl methacrylate were charged and purged with nitrogen, 5 parts by weight of 1,3-butadiene was further charged and stirring was started slowly. The solution temperature was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2]. The solid content concentration of the obtained polymer solution was 33.0% by weight.

Example 1 Preparation of thermosetting resin composition 100 parts by weight (solid content) of the copolymer [A-1] obtained in Synthesis Example 1 and KAYARAD D as the component [B]
100 parts by weight of PHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) and 1,1′-azobis-1-cyclohexylnitrile 5 as component [C]
Parts by weight, 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid and SH as a surfactant
0.1 parts by weight of -28PA (manufactured by Toray Silicone Co., Ltd.) are dissolved and mixed, and dissolved in diethylene glycol dimethyl ether so that the solid content concentration becomes 28% by weight.
The solution was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a solution (S-1) of the thermosetting resin composition.

(I) Formation of Coating Film Using a spinner on a SiO ₂ dip glass substrate,
After the composition solution (S-1) was applied, it was prebaked on a hot plate at 90 ° C. for 5 minutes to form a coating film having a thickness of 2.0 μm.

(Ii) Curing of the Coating Film The coating film obtained in (i) was heated in an oven at 230 ° C. for 60 minutes to cure the coating film. The heat resistance was evaluated using the substrate having the cured coating film obtained here.
Table 1 shows the results.

(Iii) Evaluation of Transparency, Thermal Discoloration Resistance and Surface Hardness In the above (i), except that a Corning 1737 (manufactured by Corning) substrate was used instead of the SiO ₂ dip glass substrate, (i), (ii) A coating film of the composition solution was formed in the same manner as in (1). The transparency, heat discoloration resistance and surface hardness were evaluated using the substrate having the obtained coating film. Table 1 shows the results.

(Iv) Evaluation of flatness In place of the SiO ₂ glass substrate used in (i) above,
A cured coating film was formed in the same manner as in the above (i) and (ii) except that an SiO ₂ wafer having a step of 1.0 μm was used. Using this, the step of the substrate was measured.
Table 1 shows the results.

(V) Evaluation of Adhesion Curing was carried out in the same manner as (iii) except that an SiO ₂ dip glass substrate was used instead of the Corning 1737 (manufactured by Corning) substrate used in (iii). A coating was formed. The adhesion was evaluated using this. Table 1 shows the results.

Example 2 Example 1 was the same as Example 1, except that ARONIX M-8060 was used instead of KAYARAD DPHA.
In the same manner as in the above, a composition solution (S-2) was prepared and evaluated.
Table 1 shows the results.

Example 3 A composition solution (S-3) was prepared in the same manner as in Example 1 except that the copolymer [A-2] was used instead of the copolymer [A-1]. ) Was prepared and evaluated. Table 1 shows the results.

[0058]

[Table 1]

[0059]

According to the present invention, the protective film satisfies various characteristics conventionally required, specifically, adhesion, surface hardness, transparency, heat resistance, and heat discoloration resistance. A thermosetting resin composition suitable as a material for forming a protective film for an optical device capable of flattening a step of a color filter can be obtained.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masayuki Endo 2--11-2 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J002 AC021 BC041 BC081 BC091 BD051 BD101 BF021 BG011 BG041 BG051 BG061 BG071 BG091 BG101 BG131 BH021 CD191 EH076 EH146 EK047 EK067 EQ017 ET007 FD146 FD157 FD200 GH00 GQ00 4J038 CA021 CC021 CC071 CC081 CC091 CD021 CD081 CF021 CG131 FA031 CG141 CG141 CH031 PB08 PB09 PC08

Claims (1)

[Claims] 1. (A) (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride, (a2) an unsaturated compound containing an epoxy group, (a3) the above (a1) and (a)
Copolymers of olefinically unsaturated compounds other than 2),
[B] A thermosetting resin composition comprising a polymerizable compound having an ethylenically unsaturated bond and [C] a compound which generates a radical by heat.