KR102237337B1 - Curable resin composition and cured film - Google Patents

Abstract

As a curable resin composition containing a resin having curability and a solvent,
As the solvent, it includes a solvent having a boiling point of 200 °C or higher,
The content of the solvent having a boiling point of 200°C or higher is 20% by mass or more of the total mass of the solvent in the curable resin composition.

Description

Curable resin composition and cured film TECHNICAL FIELD

The present invention relates to a curable resin composition and a cured film.

In recent liquid crystal display devices, in order to form a cured film such as a photo spacer or an overcoat, a curable resin composition is used. Japanese Patent Application Laid-Open No. 2010-152335 discloses a curable resin composition comprising diethylene glycol ethyl methyl ether, 3-methoxy-1-butanol and propylene glycol monomethyl ether as solvents.

The present invention includes the following inventions.

[1] As a curable resin composition containing a resin having curability and a solvent,

As the solvent, it includes a solvent having a boiling point of 200 °C or higher,

The content of the solvent having a boiling point of 200°C or higher is 20% by mass or more of the total mass of the solvent in the curable resin composition.

Curable resin composition.

[2] The curable resin composition according to [1], wherein a solvent having a boiling point of 220°C or higher is contained in an amount of 20% by mass or more of the total mass of the solvent in the curable resin composition.

[3] The curable resin composition according to [1] or [2], wherein the content of the solvent having a boiling point of 200°C or higher is 20% by mass or more and 80% by mass or less of the total mass of the solvent in the curable resin composition.

[4] The solvent having a boiling point of 200°C or higher is the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane, and triethylene glycol monobutyl ether Curable resin composition in any one of [1]-[3] which is at least 1 type selected from.

[5] The curable resin composition according to any one of [1] to [4], further comprising a solvent having a boiling point of 100°C or more and less than 170°C.

[6] The solvent having a boiling point of 100° C. or more and less than 170° C. is methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, or ethylene glycol monomethyl ether acetate. [5] The curable resin composition of the substrate.

[7] The curable resin composition according to [5] or [6], further comprising a solvent having a boiling point of 170°C or more and less than 200°C.

[8] The solvent having a boiling point of 170° C. or more and less than 200° C. is diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, or 3-methoxybutyl acetate [ The curable resin composition according to [7].

[9] As the resin having curability, a structural unit derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and ethylenic The curable resin composition according to any one of [1] to [8], comprising a copolymer having a structural unit derived from a monomer having an unsaturated bond.

[10] The curable resin composition according to [9], further comprising at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin as the resin having curability.

[11] A method for producing a cured film, including a step of applying the curable resin composition according to any one of [1] to [10] on a substrate, and a step of heating the curable resin composition after application.

[12] The method for manufacturing the substrate [11], wherein the cured film is a color filter or a protective film for a touch panel.

[13] A display device comprising a cured film obtained by the production method according to [12].

1: is a figure which shows the profile of the surface shape (the surface shape of a colored pattern, the surface shape of a cured film) of the evaluation sample of Example 1. FIG.
2: is a figure which shows the profile of the surface (surface shape of a colored pattern, the surface shape of a cured film) of an evaluation sample of Comparative Example 1. FIG.

In the present specification, the compounds exemplified as each component can be used alone or in combination of plural types unless otherwise noted.

The curable resin composition of the present invention is a curable resin composition containing a resin having curability (hereinafter, the resin may be referred to as “resin (A)”) and a solvent,

As the solvent, a solvent having a boiling point of 200°C or higher (hereinafter, the solvent may be referred to as "solvent (E1)") is included,

The content of the solvent (E1) is 20 mass% or more of the total mass of the solvent in the curable resin composition.

<Resin (A)>

The resin (A) is preferably a thermosetting resin, more preferably a resin cured with heat of 60°C or higher, and at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (the monomers Is sometimes referred to as "(a)"), a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (the monomer may be referred to as "(b)"). It is more preferable that it is a copolymer containing the structural unit derived from).

The copolymer further has (a) a structural unit derived from a monomer that is copolymerizable and does not have a cyclic ether structure having 2 to 4 carbon atoms (the monomer is sometimes referred to as "(c)"). You may have it.

The resin (A) is preferably the following resins [K1] and resins [K2].

Resin [K1]: Copolymer of (a) and (b);

Resin [K2]: A copolymer of (a) and (b) and (c).

As (a), unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[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-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups, such as cyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinate mono[2-(meth)acryloyloxyethyl], Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or more polyvalent carboxylic acids such as monophthalate [2-(meth)acryloyloxyethyl];

Unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid, etc. are mentioned.

Among these, as (a), (meth)acrylic acid, maleic anhydride, etc. are preferable, and (meth)acrylic acid is more preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. In addition, in this specification, "(meth)acryloyl" represents at least 1 type selected from the group consisting of acryloyl and methacryloyl. Notations such as "(meth)acrylic acid" and "(meth)acrylate" also have the same meaning.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond It refers to a polymerizable compound having. (b) is preferably a C2-C4 cyclic ether and a monomer having a (meth)acryloyloxy group.

As (b), for example, an oxylanyl group and a monomer having an ethylenically unsaturated bond (b1) (hereinafter sometimes referred to as ``(b1)''), an oxetanyl group and a monomer having an ethylenically unsaturated bond ( b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, referred to as "(b3)" may be mentioned).

(b1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as ``(b1-1)''), And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, it may be referred to as "(b1-2)").

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy Methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. I can.

As (b1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexyl Methyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; Daicel Chemical Industrial Co., Ltd. product), a compound represented by a formula (I), a compound represented by a formula (II), etc. are mentioned.

[In formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ^b1 and X ^b2 represent a single bond, -R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-. R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.]

Examples of the C1-C4 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1- Hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, and the like. . ^{Examples of} R b1 and R ^b2 include preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane- 1,6-diyl group, etc. are mentioned. As X ^b1 and X ^b2 , preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O-, *-CH ₂ CH ₂ -O- may be mentioned, and more preferably a single bond, *- CH ₂ CH ₂ -O- is mentioned. * Represents a bond with O.

Examples of the compound represented by formula (I) include compounds represented by any of formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I-15 ) Is preferred, and a compound represented by formula (I-1), formula (I-7), formula (I-9), or formula (I-15) is more preferred.

Examples of the compound represented by formula (II) include compounds represented by any of formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II-15 ) Is preferred, and a compound represented by formula (II-1), formula (II-7), formula (II-9), or formula (II-15) is more preferred.

The compound represented by formula (I) and the compound represented by formula (II) may each be used alone, or may be used by mixing at an arbitrary ratio. When mixed and used, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is on a molar basis, preferably from 5:95 to 95:5, more preferably from 10:90 to 90: 10, More preferably, they are 20:80-80:20.

As (b2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is preferable. Examples of (b3) include tetrahydrofurfuryl acrylate (eg, Biscoat V#150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point where reliability, such as heat resistance and chemical resistance, of the cured film obtained can be made higher. In addition, (b1-2) is more preferable from the viewpoint of excellent storage stability of the curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field, it is referred to as "dicyclopentanyl (meth)acrylate" as a common name. In addition, it is sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the relevant technical field, As a common name, it is referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (Meth)acrylic acid esters such as (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

Dicarboxylic acid diesters, such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxy ratio Cyclo[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-ene, 5,6-dihydroxybicyclo[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-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxy Bicyclo unsaturated compounds such as cicarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, 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, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide , Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene are preferred. .

In the resin [K1], the ratio of the structural units derived from each monomer is relative to all the structural units constituting the resin [K1],

Structural unit derived from (a); 5 to 60 mol%,

The structural unit derived from (b); It is preferable that it is 40-95 mol%,

Structural unit derived from (a); 10 to 50 mol%,

The structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the proportion of the structural unit constituting the resin [K1] is within the above range, the storage stability of the curable resin composition, the resulting cured film tends to be excellent in chemical resistance, heat resistance, and mechanical strength.

Resin [K1] is, for example, in the method described in the document "Experimental method of polymer synthesis" (Takayuki Otsu Publishing place: First edition of Chemical Co., Ltd. 1st edition, published on March 1, 1972) and the document It can be prepared by referring to the cited documents described.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc., are put into a reaction vessel, for example, oxygen is substituted with nitrogen to obtain a deoxygenated atmosphere, while stirring, heating and keeping warm. How to do it. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those commonly used in the art can be used. As a polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide) Etc.), and as a solvent, what is necessary is just to dissolve each monomer, and the solvent mentioned later etc. used for a curable resin composition can be mentioned.

In addition, the obtained resin may be used as it is the solution after the reaction, may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent in the curable resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is for the production of the curable resin composition, so that the production process of the curable resin composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each is among all the structural units constituting the resin [K2],

Structural unit derived from (a); 2 to 40 mol%,

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

The structural unit derived from (c); It is preferable that it is 1-65 mol%,

Structural unit derived from (a); 5 to 35 mol%,

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

The structural unit derived from (c); It is more preferable that it is 1 to 60 mol%.

In addition, the total amount of the structural unit derived from (a) and the structural unit derived from (b) is preferably 70 to 99 mol% with respect to the total number of moles of all structural units constituting the resin [K2], and 90 It is more preferable that it is -99 mol%. When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable resin composition, the resulting cured film tends to be excellent in chemical resistance, heat resistance, and mechanical strength. Resin [K2] can be manufactured by the same method as resin [K1].

As a specific example of resin [K1], the compound represented by (meth)acrylic acid/formula (I-1) (hereinafter, the compound may be abbreviated as "formula (I-1)" in some cases. Formula (I-2) A compound represented by another formula, such as a compound represented by ), is also similarly represented by an abbreviation (formula only). ) Copolymer, (meth)acrylic acid/formula (I-4) copolymer, (meth)acrylic acid/formula (I-5) copolymer, (meth)acrylic acid/formula (I-6) copolymer, (Meth)acrylic acid/copolymer of formula (I-7), (meth)acrylic acid/copolymer of formula (I-8), (meth)acrylic acid/copolymer of formula (I-9), (meth)acrylic acid/ Copolymer of formula (I-10), copolymer of (meth)acrylic acid/formula (I-11), copolymer of (meth)acrylic acid/formula (I-12), and (meth)acrylic acid/formula (I-13 ) Copolymer, a copolymer of (meth)acrylic acid/formula (I-14), a copolymer of (meth)acrylic acid/formula (I-15), a copolymer of (meth)acrylic acid/formula (II-1), (Meth)acrylic acid/copolymer of formula (II-2), (meth)acrylic acid/copolymer of formula (II-3), (meth)acrylic acid/copolymer of formula (II-4), (meth)acrylic acid/ Copolymer of formula (II-5), copolymer of (meth)acrylic acid/formula (II-6), copolymer of (meth)acrylic acid/formula (II-7), and (meth)acrylic acid/formula (II-8) ) Copolymer, a copolymer of (meth)acrylic acid/formula (II-9), a copolymer of (meth)acrylic acid/formula (II-10), a copolymer of (meth)acrylic acid/formula (II-11), (Meth)acrylic acid/copolymer of formula (II-12), (meth)acrylic acid/copolymer of formula (II-13), (meth)acrylic acid/copolymer of formula (II-14), (meth)acrylic acid/ Copolymer of formula (II-15), copolymer of (meth)acrylic acid/formula (I-1)/formula (II-1), (meth)acrylic acid/formula (I-2)/formula (II-2) Copolymer of, (meth)acrylic acid/formula (I-3)/formula (I Copolymer of I-3), copolymer of (meth)acrylic acid/formula (I-4)/formula (II-4), copolymer of (meth)acrylic acid/formula (I-5)/formula (II-5) Coalescence, copolymer of (meth)acrylic acid/formula (I-6)/formula (II-6), copolymer of (meth)acrylic acid/formula (I-7)/formula (II-7), (meth)acrylic acid / Formula (I-8) / formula (II-8) copolymer, (meth) acrylic acid / formula (I-9) / formula (II-9) copolymer, (meth) acrylic acid / formula (I-10 )/Copolymer of formula (II-10), (meth)acrylic acid/copolymer of formula (I-11)/formula (II-11), (meth)acrylic acid/formula (I-12)/formula (II- 12) copolymer, (meth)acrylic acid/formula (I-13)/formula (II-13) copolymer, (meth)acrylic acid/formula (I14)/formula (II-14) copolymer, (meth) ) Acrylic acid/formula (I-15)/formula (II-15) copolymer, (meth)acrylic acid/formula (I-1)/formula (I-7) copolymer, (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), and crotonic acid/formula (I-3) Copolymer, crotonic acid/copolymer of formula (I-4), crotonic acid/copolymer of formula (I-5), crotonic acid/copolymer of formula (I-6), crotonic acid/formula (I-7 ) Copolymer, crotonic acid/copolymer of formula (I-8), crotonic acid/copolymer of formula (I-9), crotonic acid/copolymer of formula (I-10), crotonic acid/formula (I -11) copolymer, crotonic acid/copolymer of formula (I-12), crotonic acid/copolymer of formula (I-13), crotonic acid/copolymer of formula (I-14), crotonic acid/formula (I-15) Copolymer, crotonic acid/copolymer of formula (II-1), crotonic acid/copolymer of formula (II-2), crotonic acid/copolymer of formula (II-3), crotonic acid /Copolymer of formula (II-4), crotonic acid/copolymer of formula (II-5), crotonic acid/copolymer of formula (II-6), crotonic acid/copolymer of formula (II-7), Crotonic acid/copolymer of formula (II-8), crotonic acid /Copolymer of formula (II-9), crotonic acid/copolymer of formula (II-10), crotonic acid/copolymer of formula (II-11), and crotonic acid/copolymer of formula (II-12), Crotonic acid/formula (II-13) copolymer, crotonic acid/formula (II-14) copolymer, crotonic acid/formula (II-15) copolymer, maleic acid/formula (I-1) copolymer Copolymer, maleic acid/formula (I-2) copolymer, maleic acid/formula (I-3) copolymer, maleic acid/formula (I-4) copolymer, maleic acid/formula (I-5) Copolymer, maleic acid/formula (I-6) copolymer, maleic acid/formula (I-7) copolymer, maleic acid/formula (I-8) copolymer, maleic acid/formula (I- 9) copolymer, maleic acid/formula (I-10) copolymer, maleic acid/formula (I-11) copolymer, maleic acid/formula (I-12) copolymer, maleic acid/formula ( I-13) copolymer, maleic acid/formula (I-14) copolymer, maleic acid/formula (I-15) copolymer, maleic acid/formula (II-1) copolymer, maleic acid/ Copolymer of formula (II-2), maleic acid/copolymer of formula (II-3), maleic acid/copolymer of formula (II-4), maleic acid/copolymer of formula (II-5), male Acid/formula (II-6) copolymer, maleic acid/formula (II-7) copolymer, maleic acid/formula (II-8) copolymer, maleic acid/formula (II-9) copolymer , Maleic acid/formula (II-10) copolymer, maleic acid/formula (II-11) copolymer, maleic acid/formula (II-12) copolymer, maleic acid/formula (II-13) Copolymer, maleic acid/copolymer of formula (II-14), maleic acid/copolymer of formula (II-15), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1), (meth ) Acrylic acid/maleic anhydride/formula (I-2) copolymer, (meth)acrylic acid/maleic anhydride/formula (I-3) copolymer, (meth)acrylic acid/maleic anhydride/formula (I-4 ) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-6), (meth)acrylic acid/maleic acid Anhydride/formula Copolymer of (I-7), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-9), (meth) Acrylic acid/maleic anhydride/formula (I-10) copolymer, (meth)acrylic acid/maleic anhydride/formula (I-11) copolymer, (meth)acrylic acid/maleic anhydride/formula (I-12) Copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-13), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-14), (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), ( Copolymer of meth)acrylic acid/maleic anhydride/formula (II-3), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-4), (meth)acrylic acid/maleic anhydride/formula (II- Copolymer of 5), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-6), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-7), (meth)acrylic acid/male Acid anhydride/copolymer of formula (II-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-9), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-10) , (Meth)acrylic acid/maleic anhydride/formula (II-11) copolymer, (meth)acrylic acid/maleic anhydride/formula (II-12) copolymer, (meth)acrylic acid/maleic anhydride/formula ( II-13) copolymer, (meth)acrylic acid/maleic anhydride/formula (II-14) copolymer, (meth)acrylic acid/maleic anhydride/formula (II-15) copolymer, etc. are mentioned. .

As a specific example of resin [K2], a copolymer of (meth)acrylic acid/formula (I-1)/methyl (meth)acrylate, (meth)acrylic acid/formula (I-2)/methyl (meth)acrylate Copolymer of, (meth)acrylic acid/formula (I-3)/methyl(meth)acrylate, (meth)acrylic acid/formula (I-4)/methyl(meth)acrylate copolymer, (meth) ) Acrylic acid / formula (I-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I -7)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-8)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-9)/methyl( Copolymer of meth)acrylate, copolymer of (meth)acrylic acid/formula (I-10)/methyl (meth)acrylate, copolymer of (meth)acrylic acid/formula (I-11)/methyl (meth)acrylate Copolymer, (meth)acrylic acid/formula (I-12)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-13)/methyl(meth)acrylate copolymer, (meth)acrylic acid / Formula (I-14) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1 )/Methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-2)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-3)/methyl(meth) Acrylate copolymer, (meth)acrylic acid/formula (II-4)/methyl (meth)acrylate copolymer, (meth)acrylic acid/formula (II-5)/methyl (meth)acrylate copolymer, (Meth)acrylic acid/formula (II-6)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-7)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-8)/Methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-9)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-10)/ A copolymer of methyl (meth)acrylate, a copolymer of (meth)acrylic acid/formula (II-11)/methyl(meth)acrylate, (meth)acrylate T) acrylic acid / formula (II-12) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula ( II-14)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II-15)/methyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-1)/dish Copolymer of clofentanyl (meth)acrylate, copolymer of (meth)acrylic acid/formula (II-1)/dicyclopentanyl (meth)acrylate, (meth)acrylic acid/formula (I-1)/formula (II) -1)/dicyclopentanyl (meth)acrylate copolymer, crotonic acid/formula (I-1)/dicyclopentanyl (meth)acrylate copolymer, maleic acid/formula (I-1)/dicyclo Copolymer of fentanyl (meth)acrylate, (meth)acrylic acid/maleic anhydride/formula (I-1)/copolymer of dicyclopentanyl (meth)acrylate, (meth)acrylic acid/formula (I-1)/ Copolymer of methyl (meth)acrylate/dicyclopentanyl (meth)acrylate, copolymer of crotonic acid/formula (II-1)/dicyclopentanyl (meth)acrylate, maleic acid/formula (II-1) /Dicyclopentanyl(meth)acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/dicyclopentanyl(meth)acrylate copolymer, (meth)acrylic acid/formula (II- 1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1)/phenyl (meth)acrylate copolymer, (meth)acrylic acid/formula (I-1)/formula (II-1)/phenyl (meth)acrylate copolymer, crotonic acid/formula ( I-1)/phenyl(meth)acrylate copolymer, maleic acid/formula (I-1)/phenyl(meth)acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1) /Phenyl(meth)acrylate copolymer, (meth)acrylic acid/formula (I-1)/methyl(meth)acrylate/phenyl(meth)acrylate copolymer, crotonic acid/formula (II-1)/ Copolymer of phenyl (meth)acrylate, copolymer of maleic acid/formula (II-1)/phenyl (meth)acrylate , (Meth)acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) Acrylate copolymer, (meth)acrylic acid/formula (I-1)/diethyl maleate copolymer, (meth)acrylic acid/formula (II-1)/diethyl maleate copolymer, (meth)acrylic acid/formula Copolymer of (I-1)/formula (II-1)/diethyl maleate, copolymer of crotonic acid/formula (I-1)/diethyl maleate, maleic acid/formula (I-1)/diethyl maleate Of (meth)acrylic acid/maleic anhydride/formula (I-1)/diethyl maleate, (meth)acrylic acid/formula (I-1)/methyl (meth)acrylate/diethyl maleate Copolymer, a copolymer of crotonic acid/formula (II-1)/diethyl maleate, a copolymer of maleic acid/formula (II-1)/diethyl maleate, (meth)acrylic acid/maleic anhydride/formula (II- 1)/diethyl maleate copolymer, (meth)acrylic acid/formula (II-1)/methyl (meth)acrylate/diethyl maleate copolymer, (meth)acrylic acid/formula (I-1)/2- Hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/formula (II-1)/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/formula (I-1)/ Copolymer of formula (II-1)/2-hydroxyethyl (meth)acrylate, copolymer of crotonic acid/formula (I-1)/2-hydroxyethyl (meth)acrylate, maleic acid/formula ( I-1)/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1)/2-hydroxyethyl (meth)acrylate copolymer, ( Copolymer of meth)acrylic acid/formula (I-1)/methyl (meth)acrylate/2-hydroxyethyl (meth)acrylate, crotonic acid/formula (II-1)/2-hydroxyethyl (meth) Acrylate copolymer, maleic acid/formula (II-1)/2-hydroxyethyl (meth)acrylate copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/2-hydroxy A copolymer of ethyl (meth)acrylate, a copolymer of (meth)acrylic acid/formula (II-1)/methyl (meth)acrylate/2-hydroxyethyl (meth)acrylate, Copolymer of (meth)acrylic acid/formula (I-1)/bicyclo[2.2.1]hept-2-ene, (meth)acrylic acid/formula (II-1)/bicyclo[2.2.1]hept-2 Copolymer of -ene, copolymer of (meth)acrylic acid/formula (I-1)/formula (II-1)/bicyclo[2.2.1]hept-2-ene, crotonic acid/formula (I-1) /Bicyclo[2.2.1]hept-2-ene copolymer, maleic acid/formula (I-1)/bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid/maleic acid Copolymer of anhydride/formula (I-1)/bicyclo[2.2.1]hept-2-ene, (meth)acrylic acid/formula (I-1)/methyl(meth)acrylate/bicyclo[2.2.1 ]Hept-2-ene copolymer, crotonic acid/formula (II-1)/bicyclo[2.2.1]hept-2-ene copolymer, maleic acid/formula (II-1)/bicyclo[2.2 .1]Hept-2-ene copolymer, (meth)acrylic acid/maleic anhydride/formula (II-1)/bicyclo[2.2.1]hept-2-ene copolymer, (meth)acrylic acid/formula Copolymer of (II-1)/methyl(meth)acrylate/bicyclo[2.2.1]hept-2-ene, copolymer of (meth)acrylic acid/formula (I-1)/N-cyclohexylmaleimide , (Meth)acrylic acid/formula (II-1)/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/formula (I-1)/formula (II-1)/N-cyclohexylmaleimide copolymer Coalescence, copolymer of crotonic acid/formula (I-1)/N-cyclohexylmaleimide, copolymer of maleic acid/formula (I-1)/N-cyclohexylmaleimide, (meth)acrylic acid/maleic anhydride /Copolymer of formula (I-1)/N-cyclohexylmaleimide, (meth)acrylic acid/Copolymer of formula (I-1)/methyl (meth)acrylate/N-cyclohexylmaleimide, crotonic acid/ Formula (II-1)/N-cyclohexylmaleimide copolymer, maleic acid/formula (II-1)/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/maleic anhydride/formula (II- 1)/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/formula (II-1)/methyl(meth)acrylate/N-cyclohexylmaleimide copolymer, (meth)acrylic acid/formula (I -1)/styrene copolymer, (meth)acrylic acid/formula (II-1)/styrene copolymer , (Meth)acrylic acid/formula (I-1)/formula (II-1)/styrene copolymer, crotonic acid/formula (I-1)/styrene copolymer, maleic acid/formula (I-1)/ Styrene copolymer, (meth)acrylic acid/maleic anhydride/formula (I-1)/styrene copolymer, (meth)acrylic acid/formula (I-1)/methyl(meth)acrylate/styrene copolymer, Copolymer of crotonic acid/formula (II-1)/styrene, 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)/methyl(meth)acrylate/styrene copolymer, (meth)acrylic acid/formula (I-1)/N-cyclohexylmaleimide/styrene copolymer, ( Copolymer of meth)acrylic acid/formula (II-1)/N-cyclohexylmaleimide/styrene, (meth)acrylic acid/formula (I-1)/formula (II-1)/N-cyclohexylmaleimide/styrene A copolymer of crotonic acid/formula (I-1)/N-cyclohexylmaleimide/styrene, a copolymer of maleic acid/formula (I-1)/N-cyclohexylmaleimide/styrene, (meth ) Acrylic acid/maleic anhydride/formula (I-1)/N-cyclohexylmaleimide/styrene copolymer, (meth)acrylic acid/formula (I-1)/methyl(meth)acrylate/N-cyclohexylmalei Mid/styrene copolymer, crotonic acid/formula (II-1)/N-cyclohexylmaleimide/styrene copolymer, maleic acid/formula (II-1)/N-cyclohexylmaleimide/styrene copolymer , (Meth)acrylic acid/maleic anhydride/formula (II-1)/N-cyclohexylmaleimide/styrene copolymer, (meth)acrylic acid/formula (II-1)/methyl(meth)acrylate/N- And copolymers of cyclohexyl maleimide/styrene.

Resin (A) has a weight average molecular weight in terms of polystyrene, preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight of the resin (A) is within the above range, there is a tendency that the coatability of the curable resin composition becomes good. The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the resulting cured film tends to be excellent in chemical resistance.

The acid value of the resin (A) is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, more preferably 40 mg-KOH/g or more and 150 mg-KOH/g or less, even more preferably It is 50 mg-KOH/g or more and 135 mg-KOH/g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the resulting cured film tends to be excellent in adhesion to the substrate.

The content of the resin (A) is preferably 30 to 90 mass%, more preferably 35 to 80 mass%, and still more preferably 40 to 70 mass% with respect to the solid content of the curable resin composition of the present invention. . When the content of the resin (A) is within the above range, the resulting cured film tends to be excellent in heat resistance, and also excellent in adhesion to the substrate and in chemical resistance. Here, the solid content of the curable resin composition refers to the amount excluding the content of the solvent (E) from the total amount of the curable resin composition of the present invention.

In the curable resin composition of the present invention, as the resin (A), at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter, the resin is referred to as ``epoxy resin ( C)” may be included.

It is preferable that the curable resin composition of the present invention further contains at least one component selected from the group consisting of a reactive monomer (B), an antioxidant (F), and a surfactant (H).

The curable resin composition of the present invention further comprises at least one compound selected from the group consisting of a polymerization initiator (D), a polymerization initiation aid (D1), a thiol compound (T), a polyhydric carboxylic anhydride, and a polycarboxylic acid. (Hereinafter, it may be referred to as "polyvalent carboxylic acid (G)"), and at least one component selected from the group consisting of an imidazole compound (J) may be included.

<Reactive Monomer (B)>

As the reactive monomer (B), a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter, it may be referred to as ``(meth)acryloyl group'') (hereinafter, the The compound may be referred to as "(meth)acrylic compound (B1)"), a compound (B2) represented by formula (1) described later, and the like.

The (meth)acrylic compound (B1) may be a (meth)acrylic compound having one (meth)acryloyl group or a (meth)acrylic compound having two or more (meth)acryloyl groups.

Examples of the (meth)acrylic compound having one (meth)acryloyl group include the same compounds as those exemplified as (a), (b) and (c), and among them, (meth)acrylic acid ester Is preferred.

Examples of the (meth)acrylic compound having two (meth)acryloyl groups include 1,3-butanedioldi(meth)acrylate, 1,3-butanediol(meth)acrylate, and 1,6-hexanedioldi(meth)acrylate. )Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl Glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, etc. are mentioned.

Examples of (meth)acrylic compounds having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanu Rate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth) )Acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripenta Erythritolhepta(meth)acrylate, tripentaerythritolocta(meth)acrylate, reactant of pentaerythritoltri(meth)acrylate and acid anhydride, reactant of dipentaerythritol penta(meth)acrylate and acid anhydride , Tripentaerythritol hepta (meth) acrylate and acid anhydride reaction product, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2- Hydroxyethyl) isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol penta(meth)acrylate, caprolactone modified dipentaerythritol hexa (Meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate, caprolactone modified tripentaerythritol penta(meth)acrylate, caprolactone modified tripentaerythritol hexa(meth)acrylate, caprolactone Modified tripentaerythritol hepta(meth)acrylate, caprolactone modified tripentaerythritol octa(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride reaction product, caprolactone modified dipentaeryth And a reaction product of ritolpenta(meth)acrylate and an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritolhepta(meth)acrylate and an acid anhydride.

As the (meth)acrylic compound (B1), a (meth)acrylic compound having three or more (meth)acryloyl groups is preferable, and dipentaerythritol hexa(meth)acrylate is more preferable.

When the curable resin composition of the present invention contains a (meth)acrylic compound (B1), the content is preferably 20 to 100 parts by mass, more preferably 25 parts by mass, based on 100 parts by mass of the resin (A). It is-70 parts by mass. When the content of the (meth)acrylic compound is within the above range, the chemical resistance and mechanical strength of the resulting cured film can be improved.

Compound (B2) is represented by formula (1).

[In formula (1), R ¹ , R ^2, and R ³ each independently represent a group represented by formula (a) or a group represented by formula (b).]

[In formulas (a) and (b), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.]

As the C1-C8 alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an octyl group, etc. are mentioned. R ⁴ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ⁵ is preferably a hydrogen atom or a methyl group.

It is preferable that at least one of R ¹ , R ² and R ³ is a group represented by formula (a).

Examples of the compound (B2) include compounds represented by formulas (1-1) to (1-7). Preferably, it is a compound represented by formula (1-1)-formula (1-4).

When the curable resin composition of the present invention contains the compound (B2), the content is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass based on 100 parts by mass of the resin (A). to be. When the content of the compound (B2) is within the above range, the heat resistance of the resulting cured film can be improved.

<Epoxy resin (C)>

The epoxy resin (C) is at least one species selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized by reacting epichlorhydrin with a phenol compound, a polyhydric alcohol, or the like. As glycidyl ether type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, trishydride And oxyphenylmethane type epoxy resins.

The glycidyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure, and is synthesized by reacting epichlorhydrin with a carbonyl group such as a phthalic acid derivative or a fatty acid. Examples of the glycidyl ester type epoxy resin include glycidyl ester type epoxy resins derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, and terephthalic acid.

In the curable resin composition of the present invention, the epoxy resin (C) is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, an o-cresol novolak type epoxy resin, a polyphenol type epoxy resin, etc. It is preferable that it is a glycidyl ether type epoxy resin of. Among them, a bisphenol A type epoxy resin is particularly preferred.

The glycidyl ether type epoxy resin can be synthesized by condensing a corresponding phenol compound and epichlorhydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by a method conventionally known to those skilled in the art. Moreover, you may use a commercial item.

Commercially available products of bisphenol A epoxy resin include jER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (manufactured by Mitsubishi Chemical Co., Ltd.) ) And the like.

As a commercial item of the bisphenol F type epoxy resin, Epicoat 807 (made by Mitsubishi Chemical Co., Ltd.), YDF-170 (made by Toto Chemical Co., Ltd.), etc. are mentioned.

Commercially available phenol novolac epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN-201, PPN-202 (manufactured by Nippon Explosives Co., Ltd.), DEN-438 (Dow Chemical Co., Ltd. Manufacturing) and the like.

Commercially available products of o-cresol novolac type epoxy resin include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Explosives Co., Ltd.), and the like.

As a commercial item of a polyphenol type epoxy resin, Epicoat 1032H60, Epicoat YX-4000 (made by Mitsubishi Chemical Co., Ltd.) etc. are mentioned.

The epoxy equivalent of the epoxy resin (C) is preferably 100 to 500 g/eq, more preferably 150 to 400 g/eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. The epoxy equivalent can be measured, for example, by a method specified in JIS K7236.

The acid value of the epoxy resin (C) is usually less than 30 mg-KOH/g, and preferably 10 mg-KOH/g or less. Moreover, the weight average molecular weight of the epoxy resin (C) becomes like this. Preferably it is 300 to 10,000, More preferably, it is 400 to 6,000, More preferably, it is 500 to 4,800.

When the curable resin composition of the present invention contains an epoxy resin (C), the content is preferably 1 to 60 parts by mass with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), More preferably, it is 5-50 mass parts. When the content of the epoxy resin (C) is within the above range, the resulting cured film tends to be excellent in adhesion to the substrate.

<Polymerization initiator (D)>

As the polymerization initiator (D), a known polymerization initiator can be used without any particular limitation as long as it is a compound capable of generating an active radical, an acid, etc. by the action of light or heat and initiating polymerization.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound is preferable, and O -A polymerization initiator containing an acyloxime compound is more preferable. These polymerization initiators tend to have high sensitivity and increase the transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by formula (d1). Hereinafter, * represents a bonding hand.

As an O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanyl Phenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-( 3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Bazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial items such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (manufactured by ADEKA) may be used.

The alkylphenone compound is a compound having a structure represented by formula (d2) or a structure represented by formula (d3). Among these structures, the benzene ring may have a substituent.

As a compound having a structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl] Butan-1-one is mentioned. Commercial items such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF) may be used. Further, a polymerization initiator having a group capable of causing chain transfer described in Japanese Laid-Open Patent Publication No. 2002-544205 may be used. As a compound having a structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( Oligomer of 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone, and benzyldimethylketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

As a triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) -6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4 -Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-) 2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5- Triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro Romethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A commercial item such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.) may be used.

As a biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Laid-Open Patent Publication No. Hei 6-75372, Japanese Laid-Open Patent Publication No. Hei 6-75373, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimi Dazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetra(trialkoxyphenyl)biimidazole (refer to Japanese Patent Laid-Open No. 48-38403, Japanese Laid-open Patent No. 62-174204, etc.), 4,4'5,5'- And imidazole compounds in which the phenyl group at the position is substituted with a carboalkoxy group (refer to Japanese Laid-Open Patent Publication No. Hei 7-10913, etc.).

In addition, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4- Phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds of; 9,10-phenanthrenequinone, 2-ethylanthraquinone, quinone compounds such as camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. Can be lifted. It is preferable to use these in combination with the polymerization initiation aid (D1) (particularly, an amine compound) mentioned later.

As the polymerization initiator (D), an acid generator can also be used. As an acid generator, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodine Onium salts, such as niumhexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

When the curable resin composition of the present invention contains a polymerization initiator (D), the content is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), More preferably, it is 0.5-15 mass parts, More preferably, it is 1-8 mass%. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity is improved, and the visible light transmittance of the obtained pattern tends to be high.

<Polymerization initiation aid (D1)>

The polymerization initiation aid (D1) is used together with the polymerization initiator (D), and polymerization of the reactive monomer (B) (e.g., (meth)acrylic compound (B1)) in which polymerization was initiated by the polymerization initiator (D) It is a compound or a sensitizer used to promote.

As a polymerization initiation aid (D1), a thiazolin compound, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the thiazolin compound include compounds represented by formulas (III-1) to (III-3) and compounds described in JP 2008-65319 A.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoic acid, and 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name, Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4 , 4'-bis(ethylmethylamino)benzophenone, etc. are mentioned. Among them, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (manufactured by Hodogaya Chemical Industries, Ltd.).

As an alkoxyanthracene compound, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy thioxanthone, etc. are mentioned. I can.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

When the curable resin composition of the present invention contains a polymerization initiation aid (D1), the content is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B), More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation aid (D1) is within the above range, there is a tendency to become more sensitive when forming a pattern.

<thiol compound (T)>

The thiol compound (T) is a compound having a sulfanyl group (-SH) in a molecule. Among them, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to a carbon atom of an aliphatic hydrocarbon structure is more preferable. It is preferable that the thiol compound (T) is contained together with the polymerization initiator (D).

As a thiol compound (T), for example, hexanedithiol, decanedithiol, 1,4-bis(methylsulfanyl)benzene, butanediolbis(3-sulfanylpropionate), butanediolbis(3-sulfanyl) Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylol propane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propane tris (3-sulfanyl propionate) ), trimethylolpropanetris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3- Sulfanylpropionate), pentaerythritol tetrakis(3-sulfanylbutyrate), and 1,4-bis(3-sulfanylbutyloxy)butane.

When the curable resin composition of the present invention contains a thiol compound (T), the content is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass, based on 100 parts by mass of the content of the polymerization initiator (D). It is a mass part. When the content of the thiol compound (T) is within the above range, the sensitivity tends to increase and developability tends to be improved.

<Antioxidant (F)>

As antioxidant (F), a phenol type antioxidant, a sulfur type antioxidant, a phosphorus type antioxidant, and an amine type antioxidant are mentioned. Among them, a phenolic antioxidant is preferred from the viewpoint of less coloring of the cured film.

As a phenolic antioxidant, for example, 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, 3,9-bis[2-{3-(3-tert-butyl-4 -Hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert- Butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'- (Mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2 ,6-di-tert-butyl-4-methylphenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert -Butyldibenz[d,f][1,3,2]dioxaphosphine is mentioned. As the phenolic antioxidant, a commercial item may be used. As commercially available phenolic antioxidants, for example, water-milizer (registered trademark) BHT, GM, GS, GP (above, all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (above, all manufactured by BASF) are mentioned.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate. , Pentaerythrityl tetrakis (3-laurylthiopropionate) is mentioned. As the sulfur-based antioxidant, a commercial item may be used. Examples of commercially available sulfur-based antioxidants include water-tiller (registered trademark) TPL-R and TP-D (above all, manufactured by Sumitomo Chemical Co., Ltd.).

Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl)phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1 And 1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butanediphosphite. As the phosphorus antioxidant, a commercial item may be used. Commercially available phosphorus antioxidants include, for example, Irgafos (registered trademark) 168, 12, 38 (above, all manufactured by BASF), Adecastav 329K, Adecastav PEP36 (above, all Co., Ltd.) Manufactured by ADEKA).

As an amine antioxidant, for example, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclo Hexyl-p-phenylenediamine, N,N'-diphenylp-phenylenediamine, and N,N'-bis(2-naphthyl)-p-phenylenediamine. As the amine-based antioxidant, a commercial item may be used. Examples of commercially available amine-based antioxidants include water-tiller (registered trademark) BPA, BPA-M1, and 4ML (above all, manufactured by Sumitomo Chemical Co., Ltd.).

When the curable resin composition of the present invention contains an antioxidant (F), the content is preferably 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). And more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the resulting cured film tends to be excellent in heat resistance and pencil hardness.

<Surfactant (H)>

Examples of the surfactant (H) include a silicone-based surfactant having no fluorine atom (hereinafter, the surfactant is referred to as a “silicone-based surfactant”), a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. have.

As a silicone type surfactant, surfactant which has a siloxane bond is mentioned. Specifically, Toray silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: manufactured by Tore Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industries Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Joint Company Manufacturing) and the like.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Fluorinert (registered trademark) FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack (registered trademark) F142D, F171, F172, F173, F177, F183, F552, F553, F554, F555, F556, F558, F559, R30 (manufactured by DIC Co., Ltd.), FTOP (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Material Electronics Hwasung ( Note) manufacturing), Suflon (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megapack (registered trademark) R08, copper BL20, copper F475, copper F477, copper F443 (manufactured by DIC Co., Ltd.), etc. are mentioned. Preferably, Megapack (registered trademark) F475 is used.

When the curable resin composition of the present invention contains a surfactant (H), the content is 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1 It is mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (H) is within the above range, the flatness of the cured film can be improved.

<Polyhydric carboxylic acid (G)>

Polyhydric carboxylic acid (G) is at least 1 type of compound selected from the group consisting of polyhydric carboxylic anhydride and polyhydric carboxylic acid. Polyhydric carboxylic acid is a compound which has two or more carboxyl groups, and polyhydric carboxylic anhydride is an anhydride of polyhydric carboxylic acid. It is preferable that it is 3000 or less in molecular weight, and, as for polyhydric carboxylic acid (G), it is more preferable that it is 1000 or less.

Examples of the polyhydric carboxylic anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, and 2-(2octa-3-enyl)succinic anhydride. , 2-(2,4,6-trimethylnona-3-enyl)succinic anhydride, tricarbarylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride and other chain polyhydric carboxylic anhydrides ;3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornenedica Ric acid anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1 ]Hepta-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hepta-5-ene-2,3-dicarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, etc. Alicyclic polyhydric carboxylic anhydride; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3'4,4 '-Diphenylsulfone tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimelitate), glycerin tris (anhydrotrimelitate), glycerin bis (anhydrotrimelitate) monoacetate, 1,3,3a Aromatic polyvalent carboxyl, such as,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione Acid anhydride; is mentioned. Adeka Hardener EH-700 (brand name (the same as below), manufactured by ADEKA Co., Ltd.), Likaside HH, Copper-TH, Copper-MH, Copper MH-700 (manufactured by Shin Nippon Ewha Co., Ltd.), Epiconia 126, YH-306, DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

Examples of the polyhydric carboxylic acids include chain polyhydric carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyhydric carboxylic acids that induce chain polyhydric carboxylic anhydrides. ; Alicyclic polyhydric carboxylic acids such as cyclohexanedicarboxylic acid and polyhydric carboxylic acid inducing alicyclic polyhydric carboxylic anhydride; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, Aromatic polyhydric carboxylic acids, such as polyhydric carboxylic acid which induces an aromatic polyhydric carboxylic anhydride; etc. are mentioned.

Especially, since the heat resistance of a cured film is excellent and transparency in a visible light region is hard to fall, a chain-type carboxylic anhydride and an alicyclic polyhydric carboxylic anhydride are preferable, and an alicyclic polyhydric carboxylic anhydride is more desirable.

When the curable resin composition of the present invention contains a polyhydric carboxylic acid (G), the content is preferably 1 to 30 parts by mass based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). And, more preferably 2 to 20 parts by mass, still more preferably 2 to 15 parts by mass. When the content of the polyhydric carboxylic acid (G) is within the above range, the heat resistance and adhesion of the cured film are excellent.

<Imidazole compound (J)>

The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include a compound known as an epoxy curing agent. Especially, the compound represented by formula (2) is preferable.

[In formula (1), R ¹¹ represents a C1-C20 alkyl group, a phenyl group, a benzyl group, or a C2-C5 cyanoalkyl group.

R ¹² to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the hydrogen atom contained in the phenyl group are, It may be substituted with a hydroxyl group.]

As a C1-C20 alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a heptadecyl group , Undecyl group is mentioned.

As a C2-C5 cyanoalkyl group, a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group are mentioned, for example.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, and stearoyl group. Can be lifted.

Examples of the imidazole compound (J) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, and 5- Hydroxymethyl-4-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1- Benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl -2-methylimidazole, 1-(2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole , 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimida There is a pawn. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferable.

When the curable resin composition of the present invention contains an imidazole compound (J), the content is preferably 0.1 parts by mass or more and 25 parts by mass based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). They are parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, and still more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (J) is in the above range, the resulting cured film tends to be excellent in transparency in the visible light region.

<Solvent>

The curable resin composition of the present invention contains a solvent having a boiling point of 200°C or higher as the solvent. In this specification, the "solvent having a boiling point of 200°C or higher" is sometimes referred to as "solvent (E1)".

The curable resin composition of the present invention may contain, as the solvent, a solvent other than the solvent (E1) (hereinafter, the solvent may be referred to as "solvent (E2)").

It is preferable that the solvent (E1) is 220 degreeC or more. Moreover, it is preferable that the boiling point of the solvent (E1) is 300 degreeC or less.

The solvent (E2) has a boiling point of less than 200°C. It is preferable that the boiling point of the solvent (E2) is 100 degreeC or more.

When the content of the solvent (E1) is within the above range, a cured film having high surface flatness can be formed.

The cured film is usually formed through a drying step of applying a curable resin composition to a substrate and then drying to form a composition layer, and a heating step of heating the composition layer to form a cured film. The curable resin composition of the present invention enables the formation of a cured film having high surface flatness, due to the action of the solvent remaining in the composition layer during the heating process, the surface of the composition layer is easily flattened and the flattening is maintained. It is presumed that this is because the heating process is performed in the state in which it became.

Furthermore, it is estimated that by making the content of the solvent (E1) the above range, a solvent in an appropriate amount for planarization can be left in the composition layer at the time of the heating step.

The content of the solvent (E1) is preferably 80% by mass or less, and more preferably 60% by mass or less of the total mass of the solvent in the curable resin composition. By being in such a range, it is possible to prevent the solvent from remaining in the cured film after the post-baking step.

The content of the solvent (E2) is usually 20 mass% or more and less than 80 mass% of the total mass of the solvent in the curable resin composition.

As the solvent (E2), a solvent having a boiling point of 100° C. or more and less than 170° C. (hereinafter, the solvent may be referred to as “solvent (E2-1)”), and a solvent having a boiling point of 170° C. or more and less than 200° C. It is preferable to contain at least one of), a solvent (E2-1) is more preferably included, and a solvent (E2-1) and a solvent (E2-) are included. It is more preferable to include both of 2).

The content of the solvent (E2-1) is preferably 10% by mass or more, and more preferably 20% by mass or more of the total mass of the solvent in the curable resin composition.

When the curable resin composition of the present invention contains both a solvent (E2-1) and a solvent (E2-2), the ratio (by mass) of the content of the solvent (E2-1) and the solvent (E2-2) is, Solvent (E2-1): It is preferable that it is a solvent (E2-2) = 10:90-50:50.

When the curable resin composition of the present invention contains a solvent (E1) and a solvent (E2), the difference between the average boiling point of the solvent (E1) and the average boiling point of the solvent (E2) is preferably 80°C or more.

It is preferable that the average boiling point of the solvent (E2) is 170 degreeC or less. The average boiling point of the solvent is calculated from the boiling point of each solvent and its mass%. For example, the average boiling point of a solvent composed of 80 mass% of a solvent having a boiling point of 160°C and 20 mass% of a solvent having a boiling point of 180°C is 164°C (= 160°C × 0.8 + 180°C × 0.2), and the boiling point is 160°C. The average boiling point of the solvent composed of 100% by mass of the solvent is 160°C.

The solvent (E1) is not particularly limited as long as it has a boiling point of 200° C. or higher, but triethylene glycol monobutyl ether (boiling point 283° C.), dipropylene glycol monopropyl ether (boiling point 213° C.), diethylene glycol monoethyl ether (boiling point 202°C), dipropylene glycol n-butyl ether (boiling point 229°C), tripropylene glycol methyl ether (boiling point 242°C), tripropylene glycol n-butyl ether (boiling point 274°C), and other ether solvents;

1,2,3-triacetoxypropane (boiling point 260°C), 1,3-butylene glycol diacetate (boiling point 232°C), 1,6-hexanediol diacetate (boiling point 260°C), 1,4-butanediol Ester solvents such as diacetate (boiling point 232°C);

Ether ester solvents such as diethylene glycol monobutyl ether acetate (boiling point 246.7°C) and diethylene glycol monoethyl ether acetate (boiling point 217°C);

Alcohol solvents, such as 1,3-butylene glycol (boiling point 208 degreeC); etc. are mentioned.

As the solvent (E1), at least 1 selected from the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane, and triethylene glycol monobutyl ether It is preferably a species.

The solvent (E2) is not particularly limited as long as the boiling point is less than 200° C., but diethylene glycol dimethyl ether (boiling point 162° C.), diethylene glycol diethyl ether (boiling point 189° C.), and diethylene glycol ethyl methyl ether (boiling point 176 ℃), dipropylene glycol dimethyl ether (boiling point 171 ℃), ethylene glycol monomethyl ether (boiling point 125 ℃), ethylene glycol monoethyl ether (boiling point 135 ℃), propylene glycol monomethyl ether (boiling point 120 ℃), propylene glycol mono Ether solvents such as ethyl ether (boiling point 133° C.), propylene glycol monopropyl ether (boiling point 149° C.), and diethylene glycol methyl ethyl ether (boiling point 176° C.);

Ester solvents such as methyl pyruvate (boiling point 138°C), butyl propionate (boiling point 145°C), methyl lactate (boiling point 155°C), ethyl lactate (boiling point 155°C), and ethyl pyruvate (boiling point 144°C);

Ketones such as 2-heptanone (boiling point 151°C), 4-hydroxy-4-methyl-2-pentanone (boiling point 166°C), diisobutyl ketone (boiling point 168.4°C), and cyclohexanone (boiling point 155°C) solvent;

Aromatic hydrocarbon solvents such as xylene (boiling point 144°C);

Alcohol solvents such as 1-butanol (boiling point 117.6°C), 2-butanol (boiling point 98°C), and isobutanol (boiling point 108°C);

3-methoxybutyl acetate (boiling point 172°C), propylene glycol monomethyl ether acetate (boiling point 146°C), propylene glycol monoethyl ether acetate (boiling point 146°C), propylene glycol monomethyl ether propionate (boiling point 161°C), Ether ester solvents such as ethylene glycol monomethyl ether acetate (boiling point 144.5° C.), ethylene glycol monoethyl ether acetate (boiling point 156° C.), and methyl 3-methoxypropionate (boiling point 142 to 143° C.);

Amide solvents such as N,N-dimethylformamide (boiling point 153°C); and the like.

As the solvent (E2-1), methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and ethylene glycol monomethyl ether acetate are preferable, and methoxybutanol, And propylene glycol monoethyl ether acetate are more preferable.

As the solvent (E2-2), diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, and 3-methoxybutyl acetate are preferable, and diethylene glycol methyl Ethyl ether is more preferred.

The content of the solvent (E) is preferably 60 to 95 mass%, and more preferably 70 to 95 mass% with respect to the total amount of the curable resin composition of the present invention. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40 mass%, more preferably 5 to 30 mass%. When the content of the solvent (E) is in the above range, the film obtained by applying the curable resin composition tends to have high flatness.

<Other ingredients>

The curable resin composition of the present invention may further contain additives known in the art, such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, and adhesion promoters, if necessary.

Examples of the filler include glass, silica, and alumina. Examples of other high molecular compounds include thermosetting resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Examples of the thermal radical generator include 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. Examples of the ultraviolet absorber include 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole and alkoxybenzophenone. Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.

As adhesion promoters, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2-(aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(amino Ethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino And propyl triethoxysilane.

The curable resin composition of the present invention substantially does not contain colorants such as pigments and dyes. That is, in the curable resin composition of the present invention, the content of the colorant with respect to the entire composition is usually less than 1% by mass, preferably less than 0.5% by mass.

When the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and the transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is preferably 70% or more. And more preferably 80% or more.

When the curable resin composition of the present invention is used as a cured film, the average transmittance of the cured film is preferably 90% or more, and more preferably 95% or more. This average transmittance is an average value of a cured film having a thickness of 2 μm after heat curing (100 to 250° C., 5 minutes to 3 hours), measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer. to be. Accordingly, a cured film excellent in transparency in the visible light region can be provided.

<Production method of curable resin composition>

The curable resin composition of the present invention includes a resin (A) and a solvent (E1), and, if necessary, a reactive monomer (B), an epoxy resin (C), a polymerization initiator (D), and a polymerization initiation aid (D1). , Antioxidant (F), surfactant (H), polyhydric carboxylic acid (G), imidazole compound (J), solvent (E2), and other components can be produced by mixing by a known method. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 µm.

<Method of manufacturing a cured film>

The manufacturing method of the cured film of the present invention includes a step of applying the curable resin composition of the present invention described above on a substrate, and a step of heating the curable resin composition after application. Usually, the manufacturing method of the cured film of this invention includes the following steps (1)-(3).

Step (1): Step of applying the curable resin composition of the present invention to a substrate

Step (2): Step of drying the curable resin composition after application under reduced pressure to form a composition layer

Step (3): Step of heating the composition layer

Moreover, when the curable resin composition of this invention contains a polymerization initiator (D), by performing the following process, a cured film which has a pattern can be manufactured.

Step (1): Step of applying the curable resin composition of the present invention to a substrate

Step (2): Step of drying the curable resin composition after application under reduced pressure to form a composition layer

Step (2a): Step of exposing the composition layer to light through a photomask

Step (2b): Step of developing the composition layer after exposure

Step (3a): Step of heating the composition layer after development

Step (1) is a step of applying the curable resin composition of the present invention to a substrate. Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and/or a driving circuit may be formed on the substrate. The coating on the substrate is preferably performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, a dip coater, or the like.

Step (2) is a step of forming a composition layer by drying the curable resin composition after application under reduced pressure. By performing the process, volatile components such as a solvent in the curable resin composition are removed. It is preferable to perform vacuum drying in a temperature range of 20-25 degreeC under a pressure of 50-150 Pa. Heat drying (prebaking) may be performed before or after drying under reduced pressure. Heat drying is usually performed using a heating device such as an oven or a hot plate. As the temperature for heating and drying, 30 to 120°C is preferable, and 50 to 110°C is more preferable. Moreover, as a heating time, it is preferable that it is for 10 seconds-60 minutes, and it is more preferable that it is 30 seconds-30 minutes.

Step (3) is a step of heating the composition layer (post-baking). By heating, the composition layer is cured, and a cured film is formed. Heating is usually performed using a heating device such as an oven or a hot plate. As a heating temperature, 130-270 degreeC is preferable, 150-260 degreeC is preferable, and 200-250 degreeC is more preferable. When the heating temperature is 200 to 250°C, it is possible to prevent unnecessary solvents from remaining in the cured film. As a heating time, 1 to 120 minutes are preferable, and 10 to 60 minutes are more preferable.

In the present invention, when the mass of the curable resin composition applied in the step (1) is 100, the mass of the composition layer provided in the heating step is preferably 30 or more, more preferably 40 or more. , More preferably 60 or more.

From the viewpoint of improving the flatness of the cured film, the mass immediately after applying the curable resin composition is 100, and the mass after prebaking in the step (2) is preferably 18 or more, more preferably 23 or more, and the step (3) The mass after (3) becomes like this. Preferably it is 23 or less, More preferably, it is 20 or less. In addition, the mass immediately after application|coating of the curable resin composition mentioned here is the mass in the situation where evaporation of a solvent does not occur, and becomes a value substantially equal to the mass of the curable resin composition used for coating.

A vacuum drying treatment in which the curable resin composition of the present invention is applied onto a substrate so that the film thickness after heat treatment becomes 1.8 µm, and dried with a vacuum dryer at a temperature of 25°C until the degree of reduced pressure reaches 66 Pa, and temperature When the heat-drying treatment heated at 100°C for 3 minutes and the heat treatment heated for 30 minutes at a temperature of 230°C were sequentially performed, if the mass of the curable resin composition immediately after application was 100, it was after the vacuum drying treatment and further It is preferable that the mass of the curable resin composition film before the heat drying treatment is 30 or more, more preferably 40 or more, still more preferably 60 or more, and the mass of the curable resin composition film after the heat treatment is 20 or less. When the film obtained by each process satisfies the above numerical range, a cured film having high surface flatness can be formed.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. As the photomask, a light-shielding portion is formed corresponding to the portion of the composition layer to be removed. The shape of the light-shielding portion is not particularly limited, and can be selected according to the intended use. As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm can be cut using a filter that cuts this wavelength range, or light in the vicinity of 436 nm, 408 nm, and 365 nm is used, and a band pass filter that extracts these wavelength ranges is used. Then, it may be selectively taken out. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

It is preferable to use an exposure apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate parallel light rays on the entire exposure surface or to accurately align the photomask and the composition layer.

Step (2b) is a step of developing the composition layer after exposure. By developing by contacting the exposed composition layer with the developer, the unexposed portion of the composition layer is dissolved and removed in the developer, thereby forming a composition layer having a pattern on the substrate. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, and a spray method. Further, the substrate may be tilted at an arbitrary angle during development. After image development, it is preferable to wash with water.

Step (3a) is a step of heating the composition layer after image development. By heating in the same manner as in the above step (3), the composition layer having the pattern is cured, and a cured film having the pattern is formed on the substrate.

Since the cured film thus obtained is excellent in surface flatness, it is useful, for example, as a protective film or an overcoat of a liquid crystal display device, a color filter substrate used for an organic EL display device or electronic paper, and a touch panel. Accordingly, it becomes possible to manufacture a display device provided with a high-quality cured film. Also in the color filter substrate having the irregularities of the colored pattern on the surface, the flatness of the surface can be improved by forming an overcoat with the curable resin composition of the present invention. The film thickness of the overcoat layer (when the surface to be coated has irregularities, the thickness from the surface of the convex portion) is preferably 0.5 µm or more and 5 µm or less, more preferably 0.5 µm or more and 3 µm or less, and the surface to be coated has irregularities. In the case of having, it is preferable that it is 30% or more of the difference in height of the unevenness of the surface to be coated.

According to the present invention, the flatness of the surface can be improved even with such a thin overcoat layer. By forming the overcoat layer with the curable resin composition of the present invention, the difference in height of the irregularities on the surface of the overcoat layer can be made smaller than the difference in height of the irregularities on the surface to be coated.

Example

Hereinafter, the present invention will be described in more detail by examples. Unless otherwise specified, "%" and "part" in the examples are mass% and mass parts.

[Examples 1 to 7 and Comparative Example 1]

<Preparation of curable resin composition>

Each component shown in Table 1 is mixed at the ratio shown in Table 1, and in order to improve the curvature, a fluorine-based surfactant (Megapak F554; manufactured by DIC Co., Ltd.) as an additive was added to 130 ppm with respect to the total amount of the obtained mixture. It was added in the amount of to obtain a curable resin composition.

In addition, in Table 1, the number of parts contained in the resin (A) represents parts by mass in terms of solid content, and the number of parts contained in components other than the solvent (hereinafter, the component is referred to as "solid content") is all of the resin (A). And the number of parts by mass when the total mass of the reactive monomer (B) is converted into 100 parts.

Details of each component are as follows.

Resin (A): Resin (Aa) synthesized by the following Synthesis Example 1

Epoxy resin (C): Bisphenol A type epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Co., Ltd.),

Reactive monomer (B): Compound (B2), monoallyldiglycidyl isocyanurate (MA-DGIC; manufactured by Shikoku Chemical Industries, Ltd.)

Antioxidant (F) 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H )-Trione (IRGANOX (registered trademark) 3114; manufactured by BASF) 1 part by mass of a curable resin (A) and a reactive monomer (B),

Polyhydric carboxylic acid (G): Butanetetracarboxylic acid (licarside BT-W; manufactured by Shin-Nippon Ewha Co., Ltd.),

Adhesion accelerator: N-phenyl-3-aminopropyltrimethoxysilane (silane coupling agent KBM573; Shin-Etsu Chemical Co., Ltd.),

Solvent (E1-1): 1,3-butylene glycol diacetate (BDGA) (boiling point 232°C),

Solvent (E1-2): Diethylene glycol monobutyl ether acetate (BDGAC) (boiling point 246.7°C),

Solvent (E1-3): 1,6-hexanediol diacetate (1,6-HDDA) (boiling point 260°C),

Solvent (E1-4): 1,2,3-triacetoxypropane (triacetin) (boiling point 260°C),

Solvent (E1-5): Triethylene glycol monobutyl ether (BTG) (boiling point 283°C),

Solvent (E2-1): Diethylene glycol methyl ethyl ether (EDM) (boiling point 176°C),

Solvent (E2-2): Methoxybutanol (MB) (boiling point 161°C),

Solvent (E2-3): Propylene glycol monomethyl ether acetate (PGMA) (boiling point 146°C).

The solvent (E) is mixed so that the solid content of the curable resin composition is 15% by mass, and the values of the solvents (E1-1) to (E1-5) and the solvents (E2-1) to (E2-2) are, The mass ratio (%) in the total weight of the solvent is shown.

(Synthesis Example 1)

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to obtain a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether were added and heated to 70° C. while stirring. Next, 40 parts of methacrylic acid; And 360 parts of a mixture of the monomer (I-1) and the monomer (II-1) {monomer (I-1) in the mixture: the molar ratio of the monomer (II-1) = 50:50}, A solution dissolved in 190 parts of ethylene glycol ethylmethyl ether was prepared, and this solution was dripped in a flask kept warm at 70°C over 4 hours using a dropping pump.

On the other hand, a solution in which 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethylmethyl ether was dripped into the flask over 5 hours using another dropping pump. . After the dropping of the polymerization initiator solution was completed, it 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 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the molecular weight distribution (Mw/Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH/g. It has the following structural units.

<Manufacture of evaluation substrate>

A 2 inch wide glass substrate (Eagle XG; manufactured by Corning) was washed sequentially with a neutral detergent, water, and isopropanol, and then dried. On this substrate, a colored photosensitive resin composition (a solid content of 19%. As a solid content, a pigment, an epoxy resin, an acrylic monomer, a polymerization initiator, an adhesion improving agent, and a surfactant are included in the following ratios.), the film thickness after post-baking is 2.0 It spin-coated so that it might become micrometer.

Content of each component in the colored photosensitive resin composition (ratio in solid content)

Pigment: about 40% (note: the proportion of the green pigment in the total amount of the pigment: about 90%, the proportion of the yellow colorant in the total amount of the pigment: 10%), the epoxy resin: 3%, the acrylic monomer: 14%, Polymerization initiator: 10%, adhesion improving agent: 1%, surfactant: 600 ppm

Next, in a clean oven, it prebaked for 3 minutes at 100 degreeC, and the colored composition layer was formed. After standing to cool, the distance between the colored composition layer on the substrate and the quartz glass photomask was set to 100 µm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., a light source; an ultra-high pressure mercury lamp) was used, and under an atmospheric atmosphere, 100 mJ/cm 2 It irradiated with light at the exposure amount of (365 nm standard). In addition, this light irradiation was carried out by passing the light emitted from an ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). In addition, as a photomask, a photomask for forming a line and space pattern having a line width of 30 µm was used. The colored composition layer after light irradiation was developed by immersing for 60 seconds at 23°C with an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, followed by washing with water, and post-baking for 30 minutes at 230°C in an oven. Then, a substrate for evaluation on which a colored pattern of a line and space having a line width of 30 µm was formed was prepared.

The film thickness of the formed colored pattern was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by RVAC Co., Ltd.) at a measurement width of 500 µm and a measurement speed of 10 seconds to obtain a profile of the surface shape of the colored pattern. Moreover, the average value of the film thickness of a colored pattern was computed from this profile. The average value of the film thickness was 2.0 µm.

<Production of cured film>

The curable resin compositions of Examples 1 to 7 and Comparative Example 1 were applied to the evaluation substrate by spin coating under the condition that the film thickness after post-baking (the film thickness from the surface of the colored pattern) became 1.0 µm.

Thereafter, under the conditions of a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25°C, a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) was dried under reduced pressure until the degree of reduced pressure reached 66 Pa, and hot On the plate, it was prebaked for 3 minutes at a temperature of 100°C. After standing to cool, a cured film was formed by post-baking at a temperature of 230°C for 30 minutes.

The film thickness of the cured film on the evaluation substrate was measured with a measurement width of 500 µm and a measurement speed of 10 seconds using a contact-type film thickness measuring apparatus (DEKTAK6M; manufactured by Albak Co., Ltd.) to obtain a profile of the surface shape of the cured film. As a result of calculating the average value of the film thickness of the cured film from the profile, the average value of the film thickness from the surface of the colored pattern was 1.0 µm.

<Evaluation of flatness>

In FIGS. 1 and 2, the outline of the colored pattern of Example 1 and Comparative Example 1 and the profile of the surface shape of the cured film are shown, respectively. The horizontal axis represents the position in the plane direction, and the vertical axis represents the position in the height direction. One convex portion in the profile of the outer shape of the colored pattern corresponds to one colored cell. Moreover, the average height difference of the uneven pattern on the surface of the cured film was calculated from the profile of the external shape of the obtained cured film. Table 1 shows the results.

<weight change>

A 2 inch wide glass substrate (Eagle XG; manufactured by Corning) was washed sequentially with a neutral detergent, water, and isopropanol, and then dried. On this substrate, the curable resin compositions of Examples 1 to 7 and Comparative Example 1 were spin-coated so that the film thickness after post-baking became 1.8 µm. After that, a cured film was produced in the same procedure as the production of the cured film. In the production of the cured film, the mass of the substrate immediately after applying the curable resin composition (including the mass of the coating film), the mass of the substrate after drying under reduced pressure (including the mass of the coating film), and the mass of the substrate after prebaking (application The mass of the film was measured) and the mass of the substrate after post-baking (including the mass of the cured film) was measured. With respect to the value obtained by subtracting the mass of the glass substrate from each of the measured values, the values obtained by converting the mass of the coating film immediately after applying the curable resin composition to 100 are shown in Table 1 "mass" column, respectively.

As can be seen from the values shown in Table 1, after drying, after prebaking, and after postbaking, the mass decreases as the process progresses, but the values relating to the mass of the coating film after drying are compared with each of the examples. It was higher than yes.

According to the present invention, a curable resin composition capable of forming a cured film having high surface flatness can be provided. Since the cured film obtained from the curable resin composition is excellent in flatness, it can be suitably used for a display device or the like.

Claims (13)

As a curable resin composition containing a curable resin, a solvent, and a reactive monomer,
As the solvent, it includes a solvent having a boiling point of 200 °C or higher,
The content of the solvent having a boiling point of 200°C or higher is 20% by mass or more of the total mass of the solvent in the curable resin composition. The method of claim 1,
A curable resin composition containing a solvent having a boiling point of 220° C. or higher and 20% by mass or more of the total mass of the solvent in the curable resin composition. The method according to claim 1 or 2,
The content of the solvent having a boiling point of 200°C or higher is 20% by mass or more and 80% by mass or less of the total mass of the solvent in the curable resin composition. The method according to claim 1 or 2,
The solvent having a boiling point of 200° C. or higher is selected from the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane, and triethylene glycol monobutyl ether. Curable resin composition which is at least 1 type. The method according to claim 1 or 2,
Further, a curable resin composition containing a solvent having a boiling point of 100°C or more and less than 170°C. The method of claim 5,
The solvent having a boiling point of 100° C. or more and less than 170° C. is methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, or ethylene glycol monomethyl ether acetate. . The method of claim 5,
Further, a curable resin composition containing a solvent having a boiling point of 170°C or more and less than 200°C. The method of claim 7,
The solvent having a boiling point of 170° C. or more and less than 200° C. is diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, or 3-methoxybutyl acetate. The method according to claim 1 or 2,
As the curable resin, a structural unit derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A curable resin composition comprising a copolymer having a structural unit derived from a monomer having. The method of claim 8,
The curable resin composition further comprising at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin as the resin having curability. A method for producing a cured film, comprising a step of applying the curable resin composition according to claim 1 or 2 on a substrate, and a step of heating the curable resin composition after application. The method of claim 11,
The cured film is a color filter or a protective film of a touch panel, a manufacturing method. A display device comprising a cured film obtained by the production method according to claim 11.

Images