KR20090056862A - Thermosetting resin composition - Google Patents

Abstract

A thermosetting resin composition is provided to form a film with excellent preserving stability, transparency, resistance to solvents, heat resistance, and surface hardness and to be useful for a coated layer for controlling the film thickness of the colored pattern and a transparent film for a display device. A thermosetting resin composition comprises binder resin(A), thermoplastic compound(B) and solvent(C) and excludes a photo-polymerization initiator. The binder resin(A) is a copolymer of (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and (A2) a monomer having an aliphatic polycyclic epoxy group; or a copolymer of (A1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (A2) a monomer having an aliphatic polycyclic epoxy group and (A3) a monomer which is different from the component (A1) and (A2) and can copolymerizable with the component (A1) and (A2).

Description

Thermosetting resin composition {THERMOSETTING RESIN COMPOSITION}

The present invention relates to a thermosetting resin composition.

In devices, such as a liquid crystal display device and a solid-state image sensor, members, such as a color filter board | substrate with which the colored pixel was formed in base materials, such as a glass substrate and a silicon wafer, and the array board | substrate with which the drive element and the wiring were formed, are used. These members may be subjected to severe treatment, such as being immersed in an acid or alkaline solution during the manufacturing process, or locally exposed to high temperature by sputtering when forming a drive element or wiring. For this reason, a protective film may be formed in the surface of a member in order to prevent such a member from damage from a manufacturing process.

This protective film is required to withstand the above-mentioned harsh treatment, and specifically, has excellent adhesiveness with a base material or a base so that a pattern can be formed, high surface hardness, and excellent transparency. It is required to have excellent points, solvent resistance, and excellent heat resistance.

As a thermosetting resin composition which can be used for such a protective film, the thermosetting composition containing the resin which consists of an acrylic copolymer which has an epoxy group represented by a carboxyl group and a glycidyl ether group, the polymeric compound which has an ethylenically unsaturated bond, and a thermal radical generating compound This is known (patent document 1).

[Patent Document 1] Japanese Patent Laid-Open No. 2000-119472, page 2 Left column 2 rows-8 rows

An object of the present invention is to provide a thermosetting resin composition capable of forming a coating film having excellent transparency and surface hardness.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the thermosetting resin composition of this invention can solve the above-mentioned subject.

That is, this invention provides the following [1]-[5].

[One]. Binder resin (A), a thermosetting compound (B), and a solvent (C) are contained, and it does not contain a photoinitiator, binder resin (A) is unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), It is a copolymer formed by copolymerizing the monomer (A2) which has an aliphatic polycyclic epoxy group, The monomer (A2) which has an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), an aliphatic polycyclic epoxy group, (A1) And a thermosetting resin composition which is different from (A2) and is a copolymer of monomer (A3) copolymerizable with (A1) and (A2).

[2]. The thermosetting resin composition as described in [1] whose monomer (A2) which has an aliphatic polycyclic epoxy group is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II).

[In Formula (I) and Formula (II), R respectively independently represents the C1-C4 alkyl group which may be substituted by the hydrogen atom or a hydroxyl group,

Each X independently represents a C1-6 alkylene group which may contain a single bond or a hetero atom.]

[3]. The thermosetting resin composition as described in [1] or [2] whose thermosetting compound (B) is a compound containing an unsaturated double bond.

[4]. The coating film formed using the thermosetting resin composition of [1]-[3].

[5]. The display apparatus containing the coating film of [4].

The thermosetting resin composition of this invention is excellent in storage stability, can form the coating film excellent in transparency, solvent resistance, heat resistance, and surface hardness, and is used for display apparatuses, such as an insulating film and a coating layer for matching the film thickness of a coloring pattern. It can be used for formation of a transparent film.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The thermosetting resin composition of this invention contains a binder resin (A), a thermosetting compound (B), and a solvent (C), and is a thermosetting resin composition which does not contain a photoinitiator.

The binder resin (A) is a copolymer obtained by copolymerizing an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride (A1) with a monomer (A2) having an aliphatic polycyclic epoxy group, or an unsaturated carboxylic acid and / or unsaturated Carboxylic anhydride (A1) and the monomer (A2) which has an aliphatic polycyclic epoxy group differ from (A1) and (A2), and copolymerize the monomer (A3) copolymerizable with (A1) and (A2), Comprising: Copolymer.

Specifically as said unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), For example, unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, a crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And anhydrides of the above unsaturated dicarboxylic acids;

Unsaturated mono [(meth) acryloyloxyalkyl of bivalent or more polyvalent carboxylic acids, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as?-(hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity and solubility in aqueous alkali solution. These may be individual and may be used in combination of 2 or more type.

The monomer (A2) having an aliphatic polycyclic epoxy group refers to a compound having an epoxy group in a cyclic form of an aliphatic polycyclic compound and having an unsaturated bond. Examples of the aliphatic polycyclic compounds include dicyclopentane and tricyclodecane.

As monomer (A2) which has an aliphatic polycyclic epoxy group, Preferably, at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) is mentioned.

[In Formula (I) and Formula (II), R respectively independently represents the C1-C4 alkyl group which may be substituted by the hydrogen atom or a hydroxyl group.

Each X independently represents a C1-6 alkylene group which may contain a single bond or a hetero atom.]

Specific examples of R include alkyl groups such as hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n And hydroxyl group-containing alkyl groups such as -butyl group. Especially, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

X as a single bond, alkylene groups, such as a methylene group, ethylene group, and a propylene group; Hetero atom containing alkylene groups, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group, an aminopropylene group, etc. are mentioned. Especially, Preferably, a single bond, a methylene group, ethylene group, an oxymethylene group, and an oxyethylene group are mentioned, More preferably, a single bond and an oxyethylene group are mentioned.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned, Preferably Formula (I-1), Formula (I-3), Formula (I) -5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably formula (I-1) and formula (I) -7), formula (I-9) and formula (I-15) are mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned, Preferably Formula (II-1), Formula (II-3), Formula (II) -5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably formula (II-1) and formula (II) -7), formula (II-9), and formula (II-15) are mentioned.

At least 1 type of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) can be used independently, respectively. Moreover, they can be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably in the formula (I): formula (II), 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20 : 80 to 80: 20.

As monomer (A3) copolymerizable with said (A1) and (A2) (except (A1) and (A2)), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n (Meth) acrylic acid alkyl esters such as -butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl (meth) (Meth) acrylic-acid cyclic alkylesters, such as)), dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5 2.1.0 ^2,6 ] decane-8-yl acrylate (in the art commonly known as dicyclopentanyl acrylate), dicyclopenta Acrylic acid cyclic alkyl esters such as oxyethyl acrylate and isoboroyl acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybi Cyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2- N, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl ) Bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [ 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [ 2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclo Hexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo Bicyclo unsaturated compounds such as [2.2.1] hept-2-ene and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

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, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxyheptyl, (alpha)-ethylacrylic-acid 6,7-epoxyheptyl, 0-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, etc. are mentioned.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferred in view of copolymerization reactivity and solubility in aqueous alkali solution. .

These may be individual and may be used in combination of 2 or more type.

The binder resin (A) used in the present invention is at least one of a copolymer obtained by copolymerizing (A1) and (A2) and a copolymer obtained by copolymerizing (A1), (A2) and (A3), It is preferable that the ratio of the structural component guide | induced from each exists in the following ranges in mole fraction with respect to the total number of moles of the structural component which comprises said copolymer.

Structural unit derived from (A1); 2 to 55 mol%

Structural unit derived from (A2); 2 to 95 mol%

Structural unit derived from (A3); 0-65 mol%

Moreover, it is more preferable if the ratio of said structural component is the following ranges.

Structural unit derived from (A1); 5 to 45 mol%

Structural unit derived from (A2); 5 to 80 mol%

Structural unit derived from (A3); 0-60 mol%

When said composition ratio exists in said range, storage stability, transparency, solvent resistance, heat resistance, and surface hardness tend to become favorable.

As such a copolymer, the copolymer of (meth) acrylic acid / formula (I-1), the copolymer of (meth) acrylic acid / formula (I-2), the copolymer of (meth) acrylic acid / formula (I-3), (Meth) acrylic acid / copolymer of formula (I-4), (meth) acrylic acid / copolymer of formula (I-5), (meth) acrylic acid / copolymer of formula (I-6), (meth) acrylic acid / Copolymer of formula (I-7), copolymer of (meth) acrylic acid / formula (I-8), copolymer of (meth) acrylic acid / formula (I-9), (meth) acrylic acid / formula (I-10) ), Copolymer of (meth) acrylic acid / formula (I-11), copolymer of (meth) acrylic acid / formula (I-12), copolymer of (meth) acrylic acid / formula (I-13), (Meth) acrylic acid / copolymer of formula (I-14), (meth) acrylic acid / copolymer of formula (I-15), (meth) acrylic acid / copolymer of formula (II-1), (meth) acrylic acid / Copolymer of formula (II-2), copolymer of (meth) acrylic acid / formula (II-3), copolymer of (meth) acrylic acid / formula (II-4), (meth) acrylic / Copolymer of formula (II-5), (meth) acrylic acid / copolymer of formula (II-6), (meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / formula (II- 8) copolymer, copolymer of (meth) acrylic acid / formula (II-9), copolymer of (meth) acrylic acid / formula (II-10), copolymer of (meth) acrylic acid / formula (II-11) , Copolymer of (meth) acrylic acid / formula (II-12), copolymer of (meth) acrylic acid / formula (II-13), copolymer of (meth) acrylic acid / formula (II-14), (meth) acrylic acid / Copolymer of formula (II-15), (meth) acrylic acid / formula (I-1) / copolymer of formula (II-1), (meth) acrylic acid / formula (I-2) / formula (II-2 Copolymer of (meth) acrylic acid / formula (I-3) / formula (II-3), copolymer of (meth) acrylic acid / formula (I-4) / formula (II-4), (Meth) acrylic acid / copolymer of formula (I-5) / formula (II-5), (meth) acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth) acrylic acid / formula ( I-7) / copolymer of formula (II-7), (meth) acrylic acid / formula Copolymer of (I-8) / formula (II-8), copolymer of (meth) acrylic acid / formula (I-9) / formula (II-9), (meth) acrylic acid / formula (I-10) / Copolymer of formula (II-10), copolymer of (meth) acrylic acid / formula (I-11) / formula (II-11), (meth) acrylic acid / formula (I-12) / formula (II-12) Copolymer of (meth) acrylic acid / formula (I-13) / formula (II-13), copolymer of (meth) acrylic acid / formula (I-14) / formula (II-14), ) Acrylic acid / copolymer of formula (I-15) / formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (I-7), (meth) acrylic acid / formula (I -1) / copolymer of formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / formula (I-3) Copolymer, copolymer of crotonic acid / formula (I-4), copolymer of crotonic acid / formula (I-5), copolymer of crotonic acid / formula (I-6), crotonic acid / formula (I-7) Copolymer of crotonic acid / formula (I-8), copolymer of crotonic acid / formula (I-9), air of crotonic acid / formula (I-10) Sieve, copolymer of crotonic acid / formula (I-11), copolymer of crotonic acid / formula (I-12), copolymer of crotonic acid / formula (I-13), crotonic acid / formula (I-14) Copolymer of, crotonic acid / copolymer of formula (I-15), copolymer of crotonic acid / formula (II-1), copolymer of crotonic acid / formula (II-2), crotonic acid / formula (II- 3) copolymer, crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / formula ( Copolymer of II-7), copolymer of crotonic acid / formula (II-8), copolymer of crotonic acid / formula (II-9), copolymer of crotonic acid / formula (II-10), crotonic acid / Copolymer of formula (II-11), copolymer of crotonic acid / formula (II-12), copolymer of crotonic acid / formula (II-13), copolymer of crotonic acid / formula (II-14), croton Copolymer of acid / formula (II-15), copolymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2), copolymer of maleic acid / formula (I-3) , Maleic acid / formula (I- 4) copolymer, maleic acid / copolymer of formula (I-5), maleic acid / copolymer of formula (I-6), maleic acid / copolymer of formula (I-7), maleic acid / formula ( I-8) copolymer, maleic acid / copolymer of formula (I-9), maleic acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), maleic acid / Copolymer of formula (I-12), copolymer of maleic acid / formula (I-13), copolymer of maleic acid / formula (I-14), copolymer of maleic acid / formula (I-15), male Acid / copolymer of formula (II-1), maleic acid / copolymer of formula (II-2), copolymer of maleic acid / formula (II-3), copolymer of maleic acid / formula (II-4) , Copolymer of maleic acid / formula (II-5), copolymer of maleic acid / formula (II-6), copolymer of maleic acid / formula (II-7), maleic acid / formula (II-8) Copolymer, maleic acid / copolymer of formula (II-9), maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11), maleic acid / formula (II-12) Copolymer of maleic acid / formula (II-13), copolymer of maleic acid / formula (II-14) Copolymer, maleic acid / copolymer of formula (II-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1), (meth) acrylic acid / maleic anhydride / formula (I-2) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic anhydride / Copolymer of formula (I-5), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-6), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-7), (meth A copolymer of acrylic acid / maleic anhydride / formula (I-8), a copolymer of (meth) acrylic acid / maleic anhydride / formula (I-9), (meth) acrylic acid / maleic anhydride / formula (I-10) Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-11), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-12), (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (I-13), (meth) acrylic acid / maleic anhydride / formula (I -14) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1), (meth) acrylic acid / Maleic anhydride / copolymer of formula (II-2), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / air of formula (II-4) Copolymer, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-5), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-6), (meth) acrylic acid / maleic anhydride / formula Copolymer of (II-7), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-8), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-9), (meth) Copolymer of acrylic acid / maleic anhydride / formula (II-10), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-11), (meth) acrylic acid / maleic anhydride / formula (II-12) Copolymers of (meth) acrylic acid / maleic anhydride / formula (II-13 Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-14), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-15), (meth) acrylic acid / formula ( Copolymer of I-1) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-2) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-3) / methyl Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, of (meth) acrylic acid / formula (I-5) / methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-7) / methyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (I-8) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-9) / methyl (meth) acrylate, (meth) acrylic acid / formula (I -10) / copolymer of methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (I-11) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-12) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-13) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate Copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (II-3) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate, (meth) acrylic acid / formula (II) -5) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-7) / methyl ( Copolymer of meth) acrylate, (meth) acrylic acid / formula (II-8) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-9) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate Copolymer of (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-12) / methyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (II-13) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate, (meth) acrylic acid / formula (II) -15) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / Copolymer of dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclopentanyl (meth) acrylate, crotonic acid / formula (I- 1) / dicyclopentanyl (meth) arc Copolymer of rate, a copolymer of maleic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acryl Copolymer of the rate, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, crotonic acid / formula (II-1) / dicyclopentanyl ( Copolymer of (meth) acrylate, copolymer of maleic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / dicyclopentanyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) Copolymer of / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1 ) / Phenyl ( Copolymer of tri) acrylate, copolymer of crotonic acid / formula (I-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / phenyl (meth) acrylate, (meth ) A copolymer of acrylic acid / maleic anhydride / formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate Copolymer, copolymer of crotonic acid / formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (II-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (I-1) / diethyl maleate, a copolymer of (meth) acrylic acid / formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / Copolymer of formula (II-1) / diethyl maleate, crotonic acid / formula Copolymer of (I-1) / diethyl maleate, copolymer of maleic acid / formula (I-1) / maleic acid ethyl, (meth) acrylic acid / maleic anhydride / formula (I-1) / male Copolymer of diethyl acid, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / dimaleic acid, and air of crotonic acid / formula (II-1) / diethyl maleate Copolymer, copolymer of maleic acid / formula (II-1) / diethyl maleate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / maleic acid diethyl, (meth) acrylic acid / formula Copolymer of (II-1) / methyl (meth) acrylate / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) Copolymer of acrylate, copolymer of crotonic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / Copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate , Copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (II-1) / 2-hydroxyethyl ( Copolymer of meth) acrylate, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / 2- Copolymer of hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene , Copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, cro Copolymer of acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene, copolymer of maleic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene , Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylic Copolymer of rate / bicyclo [2.2.1] hept-2-ene, copolymer of crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (II -1) / copolymer of bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / maleic anhydride / air of formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (I-1) / N Copolymer of -cyclohexyl maleimide, copolymer of (meth) acrylic acid / formula (II-1) / N-cyclohexyl maleimide, (meth) acrylic acid / formula (I-1) / formula (II-1) / Copolymer of N-cyclohexylmaleimide, crotonic acid / formula (I-1) / N-cycle Copolymer of hexyl maleimide, copolymer of maleic acid / formula (I-1) / N-cyclohexylmaleimide, of (meth) acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexyl maleimide Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, air of crotonic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth A copolymer of acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, a copolymer of (meth) acrylic acid / formula (I-1) / styrene, (meth) acrylic acid / formula Copolymer of (II-1) / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymer of crotonic acid / formula (I-1) / styrene, Copolymer of maleic acid / formula (I-1) / styrene, (meth) acrylic acid / mal Copolymer of leric anhydride / formula (I-1) / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / styrene, crotonic acid / formula (II-1) / styrene Copolymer of, copolymer of maleic acid / formula (II-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / styrene, (meth) acrylic acid / formula (II- 1) / Copolymer of methyl (meth) acrylate / styrene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) Copolymer of / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, crotonic acid / formula (I -1) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / formula (I-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (I -1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic Copolymer of / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, male Copolymer of acid / formula (II-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene, ( And copolymers of methacrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene.

In addition, as said notation method, said (meth) acrylic acid is acrylic acid or methacrylic acid, and methyl (meth) acrylate represents methyl acrylate or methyl methacrylate.

Said binder resin (A) is, for example, described in the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Author Publishing Co., Ltd., first chemical first edition March 1, 1972). It may be prepared with reference to the cited documents described.

Specifically, oxygen is absent by injecting a predetermined amount, a polymerization initiator, and a solvent of a compound inducing units (A1), (A2) and (A3) constituting the copolymer into the reaction vessel, and replacing oxygen with nitrogen. The polymer is obtained by stirring, heating, and keeping warm under the following. In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may take out what was taken out as solid (powder) by methods, such as reprecipitation.

The weight average molecular weight of polystyrene conversion of said binder resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of binder resin (A) exists in said range, applicability | paintability tends to become favorable and it is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, since it exists in the tendency which is excellent in developability, it is preferable.

Content of binder resin (A) used for the thermosetting resin composition of this invention is mass fraction with respect to solid content in a thermosetting resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-80 mass%, More preferably Preferably it is 20-70 mass%. When content of binder resin (A) exists in said range, storage stability, transparency, solvent resistance, heat resistance, and surface hardness tend to be favorable, and are preferable.

The thermosetting compound (B) contained in the thermosetting resin composition of this invention is a compound which has an unsaturated double bond, and can be a bifunctional monomer or a trifunctional or more than trifunctional polyfunctional monomer.

As a specific example of a bifunctional monomer, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A Bis (acryloyloxyethyl) ether, 3-methylpentanediol di (meth) acrylate, and the like.

Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, reactant of pentaerythritol tri (meth) acrylate and acid anhydride, reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone modified pentaerythritol tetra ( Meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified di Pentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa ( T) acrylate, propylene oxide modified pentaerythritol tetra (meth) acrylate, propylene oxide modified dipentaerythritol penta (meth) acrylate, propylene oxide modified dipentaerythritol hexa (meth) acrylate, and the like. . Especially, the polyfunctional monomer more than bifunctional is used preferably. These photopolymerizable compounds (B) may be individual or may be used in combination of 2 or more type.

Moreover, you may use together a monofunctional monomer so that the effect of this invention may not be impaired.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like. Can be mentioned. Moreover, (A1), (A2), (A3), etc. which are monomers of binder resin (A) are mentioned.

Content of a thermosetting compound (B) is mass fraction with respect to the total amount of binder resin (A) and a thermosetting compound (B), Preferably it is 1-70 mass%, More preferably, it is 5-65 mass%. When content of a thermosetting compound (B) exists in the said range, there exists a tendency for transparency, solvent resistance, heat resistance, surface hardness, and flatness to become favorable, and it is preferable.

The thermosetting resin composition of this invention contains a solvent (C). As said solvent (C), the various organic solvents used in the field of a thermosetting resin composition can be used. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and diethylene glycol ethyl methyl ether;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol monopropyl acetate, and diethylene glycol monobutyl acetate; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, and dipropylene glycol ethyl methyl ether;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl acetate, dipropylene glycol monopropyl acetate, dipropylene glycol monobutyl acetate;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the above solvents, organic solvents having a boiling point of 100 ° C. to 200 ° C. in the coating properties and drying properties are preferable, and alkylene glycol alkyl ether acetates, ketones, and 3- are preferably used. Esters such as ethyl ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionate and 3 Methyl methoxy propionate is mentioned.

These solvents (C) may be individual, respectively, and may be used in combination of 2 or more type.

Content of the solvent (C) in the thermosetting resin composition of this invention is 30-95 mass% normally in mass fraction with respect to a thermosetting resin composition, Preferably it is 50-90 mass%, More preferably, 55- 85 mass%. When the content of the solvent (C) is in the above range, it is applied when applied with a coating device such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), an ink jet, a roll coater, or the like. Since the castle is expected to be good, it is preferable.

The thermosetting resin composition of this invention tends to become more heat resistant further by containing antioxidant (D). As antioxidant (D), a phenolic antioxidant, sulfur type | system | group antioxidant, phosphorus antioxidant etc. are mentioned, for example.

As said phenolic antioxidant, 2-tert- butyl-6- (3-tert- butyl- 2-hydroxy-5- methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-) 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4 '-Butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl -6-tert-butylphenol), 3,9-bis [2- (3- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2 , 4,8,10-tetraoxaspiro [5 · 5] undecane, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10 Tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, triethyleneglycolbis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) prop Cypionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio)- 6- (4-hydroxy-3,5-di-tert-butyl Anilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 2,6-di-tert-butyl-4-methylphenol, etc. are mentioned.

Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, Pentaerythritol-tetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-tee Odypropionate, distearyl-3,3'- thiodipropionate, pentaerythritol- tetrakis (3-lauryl thio propionate), etc. are mentioned.

As said phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4'- butylidene-bis (3-methyl-6-tert- butylphenyl ditridecyl Phosphite, octadecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphapanthanthrene = 10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphazanthrene-10-oxide, 10-decyloxy-9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetrabisbis (2,4-di-tert- Butylphenyl) phosphite, cyclic neopentane tetraylbis (2,6-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di- tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester, phosphonic acid And bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and the like.

These antioxidants (D) may be individual, respectively, and may be used in combination of 2 or more type.

Content of antioxidant (D) used for the thermosetting resin composition of this invention is a mass fraction with respect to solid content in a thermosetting resin composition, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, 3 mass% or less. If antioxidant (D) is said mass fraction, there exists a tendency for heat resistance to be favorable.

The thermosetting resin composition of this invention does not contain a photoinitiator. By not containing a photoinitiator, the fall of the transmittance | permeability of the coating film obtained can be suppressed.

The thermosetting resin composition of this invention can also use additives (F), such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, a ultraviolet absorber, a flocculant, a chain transfer agent, as needed.

Specifically as a filler, glass, silica, alumina, etc. are illustrated.

Specific examples of other polymer compounds include thermosetting resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, and amphoteric surfactants, and the like. You may use combining the above. Examples of the above surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoi Chemical Co., Ltd.), F-Top (manufactured by Tocam Product Co., Ltd.), MegaFax (manufactured by Dainippon Ink Chemical Co., Ltd.) , Florad (manufactured by Sumitomo 3M), Asahi Guard, Saffron (above, manufactured by Asahi Glass Co., Ltd.), Sol Spas (manufactured by Geneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), PB821 (Ajinomoto Co., Ltd.) etc. are mentioned.

Specific examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N. -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercapto Propyl trimethoxysilane, etc. are mentioned.

Specific examples of the thermal radical generating agent include 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.

Moreover, sodium polyacrylate etc. are mentioned specifically as a flocculant.

Examples of the chain transfer agent include dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

After apply | coating on the base material as follows, for example, the thermosetting resin composition of this invention can form a cured coating film by heat-hardening. First, the composition is applied onto a substrate (usually glass), a color filter substrate, or an array substrate, and volatile components such as solvents are removed by vacuum drying or prebaking from the applied thermosetting resin composition layer to form a smooth coating film. Get The thickness of the coating film at this time is about 0.1-10 micrometers. The conditions for vacuum drying are 1 to 60 seconds at a vacuum degree of 50 to 300 pa. As conditions for a prebake, it is 5-180 second at 50-150 degreeC.

The cured coating film can be formed by performing the post-baking for 10 to 120 minutes at 150-230 degreeC of the coating film obtained in this way.

By using the thermosetting resin composition of this invention, a cured coating film can be formed on a board | substrate or a color filter substrate through each above processes. This cured coating film is useful as an overcoat used for a liquid crystal display device.

Therefore, by inserting the cured coating film obtained in this way into display apparatuses, such as a liquid crystal display device, the display apparatus of the outstanding quality can be manufactured with high yield.

The thermosetting resin composition of this invention is small in the viscosity change at the time of storage, and can form the coating film excellent in transparency, solvent resistance, heat resistance, and surface hardness.

The thermosetting resin composition of this invention forms the material for forming the transparent film which comprises a part of a color filter, for example, transparent films, such as an overcoat (also called a protective film), an insulating film, and the coating layer for matching the film thickness of a coloring pattern. It is preferable to use, and the coating film formed from the thermosetting resin composition of this invention is used suitably for the liquid crystal display device provided with a color filter and a color filter.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited by these Examples.

In addition, unless otherwise indicated,% and the part which show content-usage-amount in an example are a mass reference | standard.

Synthesis Example 1

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to provide a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are 50 in molar ratio. : To 50 parts by mass) and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. . On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetate, the flask over 4 hours using another dropping funnel. It dripped in the inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 32.6 mass% and an acid value of 34.3 mg-KOH / g. . The weight average molecular weight (Mw) of obtained resin Aa was 13,400, and the dispersion degree was 2.50.

Synthesis Example 2

Into a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to provide a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar ratios of 50: 50 parts by mass) and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the dissolved solution is added over 4 hours using a dropping funnel. It dripped in the flask heated at 70 degreeC. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetate, the flask over 4 hours using another dropping funnel. It dripped in the inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 32.6 mass% and an acid value of 34.2 mg-KOH / g. . The weight average molecular weight (Mw) of obtained resin Ab was 13,600, and the dispersion degree was 2.54.

Synthesis Example 3

In the same manner as in Synthesis Example 1 of JP-A-11-133600, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol dimethyl were added to a flask equipped with a cooling tube and a stirrer. 200 parts by mass of ether were injected. Subsequently, 30 mass parts of styrene, 20 mass parts of methacrylic acid, and 50 mass parts of glycidyl methacrylate were injected | thrown-in, and nitrogen-substituted, and gentle stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the resin Ac. Polystyrene conversion weight average molecular weight (Mw) of obtained resin Ac was 24,000.

Synthesis Example 4

3,4-Epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate of the synthesis example 1 (The compound represented by Formula (I-1) and the compound represented by Formula (II-1) are mixed by 50:50 by molar ratio.) A copolymer having a viscosity (23 ° C) of 120 mPa · s, a solid content of 32.8 mass%, and an acid value of 36.2 mg-KOH / g was carried out in the same manner except for changing to 3,4-epoxycyclohexylmethyl methacrylate. ) Solution was obtained. The weight average molecular weight (Mw) of obtained resin Ac was 13,900, and the dispersion degree was 2.55.

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of said binder resin, it carried out on condition of the following using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0ml / min

Detector; RI

The ratio of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into dispersion degree (Mw / Mn).

Example 1

40 parts of dipentaerythritol hexaacrylates and 1,3,5-tris (3,5-di-tert-butyl-) to 184 parts (60 parts of solid content conversion) of the resin solution containing resin Aa obtained by the synthesis example 1 4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (IRGANOX3114 manufactured by Chiba Japan Co., Ltd.) 0.8 parts propylene glycol monomethyl ether acetate 53 parts, The thermosetting resin composition 1 was obtained by mixing 20 parts of 3-ethoxyethyl propionate, 37 parts of 3-methoxy 1-butanol and 87 parts of 3-methoxybutyl acetate.

In Table 1, (-) shows that the said component is not contained.

<Storage stability>

The thermosetting resin composition 1 was stored at 23 degreeC for 2 weeks, and the value which divided the viscosity of the thermosetting resin composition after storage by the viscosity of the composition before storage was expressed by%. The results are shown in Table 2.

The closer the viscosity change to 100% is, for example, in the range of 100 to 103%.

Viscosity ; It measured at 23 degreeC using the viscometer (VISCOMETER TV-30; Toki Sangyo Co., Ltd. product).

<Pencil hardness>

A glass substrate (Eagle2000; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. After spin-coating the thermosetting resin composition 1 on this glass substrate and prebaking at 100 degreeC for 3 minutes, it post-baked at 220 degreeC for 20 minutes. It was 3.0 micrometers when the film thickness of this cured coating film was measured after cooling.

About the cured coating film obtained above, pencil hardness was measured according to JISK5400. The results are shown in Table 2. The larger the number is, the better the hardness is, and 5H or more is preferable.

<Transmittance>

Film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.), using the thermosetting resin composition 1 so as to have a film thickness of 2.9 to 3.1 μm, using the same method as the cured coating film produced for measuring pencil hardness. )).

Subsequently, the obtained cured film was measured using the microscopic spectrophotometer (OSP-SP200; OLYMPUS Co., Ltd.), and measured the transmittance | permeability (%) in 400 nm, and converted into the transmittance | permeability when converted into the film thickness of 3.0 micrometers. The results are shown in Table 2.

<Contents Resistance>

The coating film manufactured by the method similar to the cured coating film manufactured in order to measure pencil hardness is immersed for 30 minutes in 30 degreeC N-methylpyrrolidone (henceforth abbreviated as NMP), and the film thickness after immersion, and The transmittance | permeability was measured and their change was calculated | required according to following Formula.

Film thickness change (%); (Film thickness after immersion (μm) / film thickness before immersion (μm)) × 100

Transmittance change (%); (Transmittance after immersion (%) / Transmission before immersion (%)) × 100

If the value of the film thickness change is close to 100%, there is no dissolution or swelling of the film, which is preferable. Moreover, since the value of the transmittance change is high, there is no coloring and it is preferable.

Adhesiveness; On the coating film after immersion in NMP, 100 squares of 1 mm per side were produced using a commercially available cutter knife. Peeling test was done using the commercially available cellophane tape. [(Number of squares left on the substrate without peeling) / 100] was obtained. If the value of [(the number of squares left on the substrate without peeling) / 100] is large, the adhesion of the film is excellent and satisfactory.

Heat resistance; The coating film manufactured by the same method as the cured coating film manufactured in order to measure pencil hardness is left to stand in a clean oven at 240 degreeC for 1 hour, and the film thickness and transmittance | permeability (measurement wavelength; 400 nm) before and after heating are measured, and it is represented by following Formula. Accordingly, their change was obtained. The results are shown in Table 2.

Film thickness change (%); (Film thickness after heating (μm) / film thickness before heating (μm)) × 100

Transmittance change (%); (Transmittance (%) after heating / transmittance (%) before heating) × 100

If the value of the film thickness change is close to 100%, there is no decomposition or the like of the film due to heating, which is preferable. Moreover, it is preferable that the value of the transmittance change is high because there is no coloring of the film.

Adhesiveness; On the coating film after heating in a heat resistance test, 100 squares of 1 mm per side were produced using a commercially available cutter knife. Peeling test was done using the commercially available cellophane tape. [(Number of squares left on the substrate without peeling) / 100] was obtained. If the value of [(the number of squares left on the substrate without peeling) / 100] is large, the adhesion of the film is excellent and satisfactory.

Example 2

The thermosetting resin composition 2 was obtained so that it might become the composition shown in Table 1, it carried out similarly to the thermosetting resin composition 1, and the evaluation was performed. The results are shown in Table 2.

Comparative Example 1

The thermosetting resin composition (3) was obtained so that it might become the composition shown in Table 1. The storage stability was measured in the same manner as in Example 1, and as a result, it was thickened, and the evaluation was stopped. Only pencil hardness was performed before the storage stability test.

Comparative Example 2

The thermosetting resin composition 4 was obtained so that it might become the composition shown in Table 1. The storage stability was measured in the same manner as in Example 1, and as a result, it was thickened, and the evaluation was stopped. Only pencil hardness was performed before the storage stability test.

Comparative Example 3

In the thermosetting resin composition 1 used in Example 1, 4 parts of B-CIM (made by Hodogaya Chemical Industry Co., Ltd.) as a photoinitiator, 0.8 parts of isopropyl thioxanthones as a sensitizer, and PEMP (Asaka Chemical Industries, Ltd. as a promoter) ) 3 parts) were added, the composition 5 was obtained, and the evaluation was performed similarly to Example 1. The results are shown in Table 2.

From the result of Examples 1-2 shown in Table 2, the thermosetting resin composition of this invention containing the binder resin which has an epoxy group of a specific structure is excellent in storage stability, and when using the thermosetting resin composition of this invention, transparency, It turns out that the coating film excellent in solvent resistance, heat resistance, and surface hardness can be formed.

On the other hand, the thermosetting resin composition which does not contain the binder resin which has the epoxy group of the specific structure disclosed in the comparative examples 1 and 2 was obtained only inferior to storage stability. Moreover, the composition of the comparative example 3 containing a photoinitiator was obtained only with the film | membrane of low transmittance | permeability and inferior transparency.

Claims (5)

Binder resin (A), a thermosetting compound (B), and a solvent (C) are contained, and it does not contain a photoinitiator, binder resin (A) is unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), It is a copolymer formed by copolymerizing the monomer (A2) which has an aliphatic polycyclic epoxy group, The monomer (A2) which has an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (A1), an aliphatic polycyclic epoxy group, (A1) And a thermosetting resin composition which is different from (A2) and is a copolymer of monomer (A3) copolymerizable with (A1) and (A2). The method of claim 1, Thermosetting resin composition whose monomer (A2) which has an aliphatic polycyclic epoxy group is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II).

[In Formula (I) and Formula (II), R respectively independently represents the C1-C4 alkyl group which may be substituted by the hydrogen atom or a hydroxyl group, Each X independently represents a C1-6 alkylene group which may contain a single bond or a hetero atom.] The method according to claim 1 or 2, Thermosetting resin composition whose thermosetting compound (B) is a compound containing an unsaturated double bond. The coating film formed using the thermosetting resin composition of any one of Claims 1-3. The display device containing the coating film of Claim 4.