TWI835726B - Curable resin composition and cured film - Google Patents

Abstract

A curable resin composition comprising: resin (A), the resin (A) being composed of a structural unit (Aa) having an α,β-unsaturated carbonyl group and an active methylene group or an active methine group A copolymer of unit (Ab); at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts and tertiary sulfonium salts; and selected from the group consisting of epoxy compounds and five-membered ring carbonate compounds at least one compound in the group.

Description

Curable resin composition and cured film

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

The Examples of Japanese Patent Application Laid-Open No. 3-172301 describe a reaction product obtained by polymerizing methyl methacrylate, ethyl methacrylate, and methacrylic acid, and then reacting glycidyl methacrylate. A composition as a resin component and a cured film obtained by curing the composition at 230°C.

The present invention includes the following contents.

[1] A curable resin composition comprising: resin (A) containing a structural unit (Aa) having an α,β-unsaturated carbonyl group and having an active methylene group or an active methylene group A copolymer of a base structural unit (Ab); at least one compound selected from the group consisting of a quaternary ammonium salt, a quaternary phosphonium salt, and a tertiary sulfonium salt (hereinafter, this compound is referred to as the "first additive") ; and at least one compound selected from the group consisting of epoxy compounds and five-membered ring carbonate compounds (hereinafter, this compound is referred to as the "second additive").

[2] A hardening resin composition as described in [1], comprising a quaternary ammonium salt and an epoxy compound.

[3] A curable resin composition as described in [1] or [2], wherein the epoxy compound is an epoxy compound having at least two oxycyclopropyl groups in one molecule.

[4] A cured film formed from the curable resin composition according to any one of [1] to [3].

In this specification, the compounds exemplified as each component can be used alone or in combination of multiple types unless otherwise specified.

[Cureable resin composition]

The curable resin composition of the present invention contains a resin (hereinafter referred to as resin (A)), a first additive, and a second additive. The curable resin composition of the present invention may further contain a solvent (hereinafter referred to as solvent (E)).

The resin (A) contains a structural unit having an α,β-unsaturated carbonyl group (hereinafter referred to as the structural unit (Aa)) and a structural unit having an active methylene group or an active methine group (hereinafter referred to as the structural unit (Ab) ) copolymer.

The first additive is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts.

The second additive is at least one compound selected from the group consisting of epoxy compounds and five-membered ring carbonate compounds.

By allowing the resin (A) to coexist with the first additive and the second additive, the resulting hardened film has excellent solvent resistance.

The curable resin composition of the present invention may also contain a polymerizable compound (hereinafter referred to as a polymerizable compound (C)). When the polymerizable compound (C) is contained, it is preferred that a polymerization initiator (hereinafter referred to as a polymerization initiator (D)) is also contained.

The curable resin composition of the present invention may also contain other components, such as a polymerization starting aid (hereinafter referred to as a polymerization starting aid (H)), a leveling agent (hereinafter referred to as a leveling agent (B)), or Colorant (hereinafter referred to as colorant (K)).

<Resin(A)>

Resin (A) has constituent units (Aa) and constituent units (Ab). Resin (A) may also contain other constituent units (hereinafter referred to as constituent units (Ac)).

The resin (A) may also contain two or more constituent units (Aa) and constituent units (Ab).

The resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of being soluble in an aqueous solution of an alkali compound, i.e., a developer. The resin (A) preferably contains a constituent unit having an acid group (hereinafter referred to as constituent unit (Ac1)) as a constituent unit (Ac). The resin (A) may also contain a constituent unit other than constituent unit (Ac1) (hereinafter referred to as constituent unit (Ac2)) as a constituent unit (Ac). Each constituent unit is described in detail below.

Furthermore, in this specification, "(meth)acrylic acid" refers to at least one compound selected from the group consisting of acrylic acid and methacrylic acid. "(meth)acryl" and "(meth)acrylate" also have the same meaning.

〔1〕Constituent unit (Aa)

In this specification, the α,β-unsaturated carbonyl group is a structure represented by -CO-CX=CX- (X independently represents an arbitrary substituent), preferably -CO-CX=CH-. X may be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, and a carboxyalkyl group having 1 to 6 carbon atoms, etc., preferably a hydrogen atom or a methyl group.

The structural unit (Aa) can be obtained, for example, by adding a compound having an α,β-unsaturated carbonyl group (hereinafter referred to as a carboxylic acid reactive compound) to a structural unit having a carboxyl group (hereinafter referred to as the structural unit (Aa')). Examples of carboxylic acid-reactive compounds include compounds having an oxiryl group and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa”)). Examples of the structural unit (Aa′) include the following structures Unit (Ac1) is a structural unit having a carboxyl group.

The structural unit (Aa) can also be obtained by reacting (meth)acrylic acid and the structural unit which has an oxiryl group, for example.

As the monomer (Aa"), there can be listed compounds having a linear or branched unsaturated aliphatic hydrocarbon cyclooxygenated structure and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa"-1)), and compounds having an unsaturated alicyclic hydrocarbon cyclooxygenated structure and an α,β-unsaturated carbonyl group (hereinafter referred to as monomer (Aa"-2)).

Examples of the monomer (Aa″-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and Glycidyl conate, etc.

Specific examples of the monomer (Aa”-2) include: 3,4-epoxycyclohexylmethyl (meth)acrylate, 5,6-epoxytricyclo [5.2.1.0 ^2,6 ]Decan-8-yl(meth)acrylate, 5,6-epoxytricyclo[5.2.1.0 ^2,6 ]Decan-8-yloxymethyl(meth)acrylate, 2,3 -Epoxycyclopentylmethyl(meth)acrylate, 2-hydroxy-3-(2,3-epoxycyclopentyloxy)cyclopentylmethyl(meth)acrylate, 3-(3 ,4-Epoxycyclohexylmethyloxycarbonyl)-6-hydroxycyclohexylmethyl(meth)acrylate, 2-hydroxy-5-(3,4-epoxycyclohexylcarbonyloxymethyl)cyclo Hexylmethyl(meth)acrylate, 3-(3,4-epoxycyclohexyl)-9-hydroxy-1,5-dioxaspiro[5,5]undecan-8-yl(methyl ) acrylate, 3-(3,4-epoxycyclohexyl)-9-hydroxy-2,4-dioxaspiro[5,5]undecan-8-yl (meth)acrylate, etc.

These may be used alone, or two or more types may be used in combination. Among these, glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate is preferably used.

For example, the structural unit (Aa) in which 3,4-epoxycyclohexylmethyl (meth)acrylate is added to the (meth)acrylic acid structural unit is represented by the formula (Aa-1).

[In formula (Aa-1), R ¹ and R ^x each independently represent a hydrogen atom or a methyl group].

For example, a constituent unit in which glycidyl (meth)acrylate is added to a (meth)acrylic acid constituent unit is represented by formula (Aa-2).

[In formula (Aa-2), R ⁵ and R ^y each independently represent a hydrogen atom or a methyl group].

As the constituent unit (Aa), the constituent unit represented by formula (Aa-1) or the constituent unit represented by formula (Aa-2) is preferred.

〔2〕Constituent unit (Ab)

As the constituent unit (Ab), for example, there can be cited constituent units that can be derived from an unsaturated compound having an active methylene group or an active methine group. The so-called constituent unit that can be derived from an unsaturated compound having an active methylene group or an active methine group refers to a constituent unit derived from the unsaturated compound obtained by polymerizing the unsaturated compound.

As unsaturated compounds that induce the constituent unit (Ab) and have an active methylene group, compounds represented by formula (I) can be cited, and as unsaturated compounds that have an active methine group, compounds represented by formula (II) can be cited.

^R11 - ^R12 - ^R13 - _CH2 - ^R14 (I)

[In formula (I) and formula (II), R ¹¹ represents a group represented by any one of formula (1-1) to formula (1-4).

^R12 represents a single bond, -X- or -XO-* (* represents a bond with ^R13 ).

R ¹³ represents -CO- or -SO ₂ -.

R ¹⁴ represents -CO-R ¹⁵ , -SO ₂ -R ¹⁵ , cyano or nitro.

X represents a divalent hydrocarbon group with 1 to 20 carbon atoms.

R ¹⁵ represents a hydrocarbon group having 1 to 24 carbon atoms or an alkoxy group having 1 to 12 carbon atoms].

[In formula (1-1) to formula (1-4), R ¹⁶ and R ¹⁸ each independently represent a hydrogen atom or a carbon number of 1 to 24 alkyl groups.

^R17 represents a alkyl group having 1 to 24 carbon atoms, and the methylene group contained in the alkyl group may be substituted by -CO- or -O-].

Examples of the alkyl group having 1 to 24 carbon atoms in R ¹⁵ to R ¹⁸ include alkyl groups such as methyl, ethyl, propyl, butyl and hexyl; and cycloalkyl groups such as cyclohexyl.

When the methylene group contained in the alkyl group in R ¹⁷ is substituted with -O- or -CO-, the alkyl group has 2 to 24 carbon atoms. Examples of the group in which the methylene group contained in the alkyl group of 2 to 24 carbon atoms is substituted with -O- or -CO- include alkoxy groups such as methoxy, ethoxy, propoxy, and hexyloxy; cycloalkoxy groups such as cyclohexyloxy; and oxo-containing alkyl groups such as 2,4-dioxopentyl, 3,5-dioxohexyl, and 1,3-dioxobutyloxyethyl.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in X include methylene, ethylidene, propanediyl, butanediyl, hexanediyl, octanediyl, decanediyl, Divalent chain aliphatic hydrocarbon groups with 1 to 20 carbon atoms such as dialkanediyl; divalent cyclic formulas with 3 to 20 carbon atoms such as cyclohexanediyl, tricyclodecanediyl, and groups represented by the following formulas Aliphatic hydrocarbon group; bivalent aromatic hydrocarbon group having 6 to 20 carbon atoms such as phenylene group, etc. Preferred examples include methylene group and ethylene group.

R ¹¹ is preferably a group represented by formula (1-1) or formula (1-4), more preferably a group represented by formula (1-1).

R ¹² represents a single bond, -X- or -XO-* (* represents a bond with R ¹³ ), and preferably X is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms.

R ¹³ is preferably -CO-.

R ¹⁴ is preferably -CO-R ¹⁵ .

R ¹⁵ is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

R ¹⁶ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group.

R ¹⁷ is preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

R ¹⁸ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom.

Specific examples of the compound represented by formula (I) include the following compounds.

As the compound represented by formula (II), specifically, the following compounds can be listed.

The compound represented by any one of formula (I-1) to formula (I-7), formula (I-16), formula (II-1) and formula (II-2) is R ¹¹ is formula (1- 1) A compound in which R ¹⁶ is a methyl group, but a compound in which the methyl group of R ¹⁶ is substituted by a hydrogen atom can also be exemplified as a compound from which the structural unit (Ab) is derived.

The structural unit (Ab) is preferably a structural unit represented by formula (Ab-1).

[In formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms].

Examples of the alkyl group having 1 to 6 carbon atoms in ^R4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl and n-hexyl.

Preferred examples of R ⁴ include a hydrogen atom and a methyl group.

Examples of compounds derived from the structural unit represented by formula (Ab-1) include 2-(1,3-dioxobutyloxy)ethyl(meth)acrylate [formula (I-1) represented compound].

〔3〕Constituent unit (Ac1)

The constituent unit (Ac1) is a constituent unit that can be derived from an unsaturated compound having an acid group. Examples of the acid group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic group. An unsaturated compound having two or more carboxyl groups may also be an acid anhydride. The constituent unit that can be derived from an unsaturated compound having an acid group refers to a constituent unit derived from the unsaturated compound in a copolymer obtained by polymerizing the unsaturated compound as a monomer. A copolymer having the constituent unit can be obtained by polymerizing an unsaturated compound having an acid group as a monomer. In addition, it can also be obtained by adding an acid anhydride to a copolymer containing a constituent unit having a hydroxyl group.

The resin (A) preferably has a constituent unit (Ac1).

As the unsaturated compound having an acid group, unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides are preferred. Specific examples of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include: (meth)acrylic acid, crotonic acid, vinylbenzoic acid, methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[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-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, α-(hydroxymethyl)(meth) acrylic acid and other unsaturated monocarboxylic acids; cis-butenedioic acid, fumaric acid, citric acid, mesaconic acid, itaconic acid, 3-hydroxy-1,2-dicarboxylic acid, ... - unsaturated dicarboxylic acids such as vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene; maleic anhydride, Unsaturated dicarboxylic anhydrides such as conic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (nadic anhydride (himic anhydride)); unsaturated mono[(meth)acryloxyalkyl] esters of polycarboxylic acids having a divalent or higher value such as mono[2-(meth)acryloxyethyl] succinate and mono[2-(meth)acryloxyethyl] phthalate; etc.

Among these, (meth)acrylic acid and maleic anhydride are preferred due to their excellent copolymerization reactivity and alkali solubility of copolymers. These can be used alone or in combination.

〔4〕Constituent unit (Ac2)

The structural unit (Ac2) is a structural unit different from the structural unit (Aa), the structural unit (Ab), and the structural unit (Ac1). The structural unit (Ac2) can be derived from a monomer that can be polymerized with a monomer from which other structural units (for example, the structural unit (Aa), the structural unit (Ab), or the structural unit (Ac1)) are derived. Specific examples of such monomers include: methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate Second butyl acrylate, third butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane -8-yl (meth)acrylate (known as "dicyclopentyl (meth)acrylate" as a common name in this technical field), tricyclo[5.2.1.0 ^2,6 ]decene-8 -(meth)acrylate (called "dicyclopentenyl (meth)acrylate" as a common name in this technical field), dicyclopentyloxyethyl (meth)acrylate, ( Isobornyl methacrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (Methyl) Acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methyl Bicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[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 - Bicyclic unsaturated compounds such as ethoxybicyclo[2.2.1]hept-2-ene and 5,6-dihydroxybicyclo[2.2.1]hept-2-ene; N-phenylmaleimide , N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinate Dicarbonyl imide compounds such as amide-4-maleimide butyrate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene , p-methoxystyrene and other styrene compounds; (meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3-butadiene, isoprene Alkene, 2,3-dimethyl-1,3-butadiene, etc.

Among them, (meth)acrylates, styrene compounds and dicarbonyl imide compounds are preferred in terms of reactivity in copolymerization or heat resistance of the copolymer, and methyl (meth)acrylate, n-butyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, styrene, vinyltoluene, N-phenyl cis-1-butylene diimide, N-cyclohexyl cis-1-butylene diimide and N-benzyl cis-1-butylene diimide are more preferred. These may be used alone or in combination.

[5] Resin (A)

The resin (A) is the following resin [K1] or resin [K2].

Resin [K1]: A copolymer comprising a constituent unit (Aa) and a constituent unit (Ab); Resin [K2]: A copolymer comprising a constituent unit (Aa), a constituent unit (Ab) and a constituent unit (Ac).

Resin (A) is preferably resin [K2]. Furthermore, the resin [K2] preferably contains the structural unit (Ac1) and the structural unit (Ac2) as the structural unit (Ac).

When the resin (A) contains the constituent unit (Ac1), its ratio relative to all the constituent units constituting the resin (A) is preferably 1 mol% to 50 mol%, and more preferably 5 mol% to 40 mol%.

When the resin (A) contains the structural unit (Ac2), the ratio is preferably 1 mol% to 70 mol%, more preferably 5 mol% with respect to all the structural units constituting the resin (A). %~60mol%.

In the resin [K1], the ratio of each structural unit is preferably 5 to 95 mol% for the structural unit (Aa) and 5 to 95 mol% for the structural unit (Ab) relative to all the structural units constituting the resin [K1]. 5 mol% to 95 mol%, more preferably the structural unit (Aa) is 30 mol% to 70 mol%, and the structural unit (Ab) is 30 mol% to 70 mol%.

If the ratio of the structural units constituting the resin [K1] is within the above range, the cured resin composition will have excellent storage stability, the heat resistance and mechanical strength of the resulting film, and further, a cured film with excellent solvent resistance can be formed. Better in terms of aspects.

In the resin [K2], regarding the ratio of each structural unit, among all the structural units constituting the resin [K2], it is preferable that the structural unit (Aa) is 5 mol% to 80 mol%, and the structural unit (Ab) is preferably 5 mol% to 80 mol%, the structural unit (Ac) is 1 mol% to 70 mol%, more preferably the structural unit (Aa) is 5 mol% to 60 mol%, and the structural unit (Ab) It is 5 mol% to 60 mol%, and the structural unit (Ac) is 3 mol% to 60 mol%.

In the resin [K2], when only the constituent unit (Ac1) is included as the constituent unit (Ac), it is preferred that the constituent unit (Aa) is 5 mol% to 80 mol%, the constituent unit (Ab) is 5 mol% to 80 mol%, the constituent unit (Ac1) is 5 mol% to 40 mol%, and it is more preferred that the constituent unit (Aa) is 5 mol% to 50 mol%, the constituent unit (Ab) is 5 mol% to 50 mol%, and the constituent unit (Ac1) is 10 mol% to 40 mol%.

In the case where the resin [K2] contains only the structural unit (Ac2) as the structural unit (Ac), it is preferable that the structural unit (Aa) is 5 to 80 mol% and the structural unit (Ab) is 5 Mol % ~ 80 mol %, the structural unit (Ac2) is 1 mol % ~ 70 mol %, more preferably the structural unit (Aa) is 5 mol % ~ 50 mol %, and the structural unit (Ab) is 5 mol% to 50 mol%, and the structural unit (Ac2) is 3 mol% to 60 mol%.

In the resin [K2], when both the structural unit (Ac1) and the structural unit (Ac2) are included as the structural unit (Ac), it is preferable that the structural unit (Aa) is 5 mol% to 50 mol%. , the structural unit (Ab) is 5 mol% to 50 mol%, the structural unit (Ac1) is 1 mol% to 50 mol%, and the structural unit (Ac2) is 1 mol% to 60 mol%, more preferably The structural unit (Aa) is 5 mol%~30 mol%, The structural unit (Ab) is 5 mol% to 30 mol%, the structural unit (Ac1) is 10 mol% to 40 mol%, and the structural unit (Ac2) is 3 mol% to 55 mol%.

When the ratio of the structural units of the resin [K2] is within the above range, the cured resin composition has excellent storage stability, the heat resistance and mechanical strength of the resulting film, and furthermore, a cured film excellent in solvent resistance can be obtained. Better.

The weight average molecular weight (Mw) of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000, and particularly preferably 5,000 to 20,000. If the weight average molecular weight (Mw) of the resin (A) is within the above range, the coating properties of the curable resin composition of the present invention tend to be improved, which is preferred.

The dispersion degree [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 dispersion degree is within the above range, the obtained cured film tends to have more excellent solvent resistance.

When the resin (A) contains the constituent unit (Ac1), the acid value (solid content conversion) 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, and further preferably 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 the resin, and can be obtained by titration using an aqueous potassium hydroxide solution. If the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion to the substrate.

Resin (A) can be derived from the monomer of the constituent unit (Aa), It is obtained by polymerizing the monomer of the structural unit (Ab) and, if necessary, the monomer from which the structural unit (Ac) is derived.

As the polymerization method, the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) can be cited.

Specifically, a method can be listed in which a specified amount of monomers for deriving constituent units (Aa), monomers for deriving constituent units (Ab), and monomers for deriving constituent units (Ac) as needed, a polymerization initiator, and a solvent are added to a reaction vessel, and a deoxygenated environment is created by replacing oxygen with nitrogen, and the mixture is heated and kept warm while being stirred.

In addition, the polymerization method may also include a polymerization reaction of a monomer derived from a structural unit (Aa'), a monomer derived from a structural unit (Ab), and, if necessary, a monomer derived from a structural unit (Ac). , and further a method of forming the structural unit (Aa) through the reaction of the structural unit (Aa') and the compound (Aa").

In addition, the polymerization initiator, solvent, etc. used in the production of resin (A) are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.), as the solvent, any solvent can be used as long as it dissolves each monomer, and examples thereof include the solvents described below used in curable resin compositions, and the like.

Furthermore, the obtained resin can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) extracted by reprecipitation or the like. In particular, by using the solvent used in the curable resin composition of the present invention as a polymerization solvent, the solution after the reaction can be directly used in the manufacture of the curable resin composition, thereby simplifying the manufacturing steps of the curable resin composition.

The content of the resin (A) in the curable resin composition of the present invention is preferably 5% to 95% by mass, more preferably 10% to 95% by mass relative to the solid content in the curable resin composition. 95% by mass. When the content rate of the resin (A) is within the above range, the resulting cured film tends to have more excellent solvent resistance. Here, the solid content in the curable resin composition refers to the component after removing the solvent from the curable resin composition. The total amount of solid content and the content of each component relative thereto can be measured, for example, by a known analysis method such as liquid chromatography or gas chromatography.

<1st additive>

The first additive is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts and tertiary stibnium salts.

[1] Quaternary ammonium salt

As quaternary ammonium salts, for example, compounds represented by formula (IV) can be cited.

[In formula (IV), R ⁴¹ to R ⁴⁴ each independently represent a alkyl group having 1 to 24 carbon atoms which may have a substituent.

Y ^z- represents an anion with z valence.

z represents an integer from 1 to 3].

Examples of the alkyl group having 1 to 24 carbon atoms in R ⁴¹ to R ⁴⁴ include an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkenyl group having 3 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and an aralkyl group having 7 to 24 carbon atoms. Preferred examples include an alkyl group having 1 to 24 carbon atoms and an aryl group having 6 to 24 carbon atoms.

The carbon number of R ⁴¹ to R ⁴⁴ is preferably 4 to 100 based on the total carbon number per molecule of the compound represented by formula (IV).

Examples of substituents that the alkyl group may have include halogen atoms, cyano groups, acyl groups, acyloxy groups, carboxyl groups, and alkoxy groups.

Examples of the cation of the compound represented by formula (IV) include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, tri-n-octylmethylammonium ion, hexadecyltrimethylammonium ion, benzyltrimethylammonium ion, benzyltriethylammonium ion, hexadecylbenzyldimethylammonium ion, phenyltrimethylammonium ion, and phenyltriethylammonium ion. Preferred examples include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, and tri-n-octylmethylammonium ion.

Examples of Y ^z- in formula (IV) include halogenide ions such as chlorine ions, fluorine ions, bromine ions, and iodine ions; sulfuric acid ions, nitric acid ions, phosphoric acid ions, perchloric acid ions, hydrogen sulfate ions, and hydroxide ions; carboxylic acid ions such as acetic acid ions, benzoic acid ions, and salicylic acid ions; benzenesulfonic acid ions, p-toluenesulfonic acid ions, and the like. ions and sulfonic acid ions such as trifluoromethanesulfonic acid ions; phenoxide ions and p-nitrophenoxide ions and other phenclate ions; tetrafluoroborate ions, hexafluorophosphate ions and tetraphenylborate ions, etc., preferably, halide ions, carboxylic acid ions, sulfonic acid ions and phenoxide ions can be listed.

The compound represented by formula (IV) includes any one selected from the above cations and any one selected from Y ^z- .

Examples of quaternary ammonium ions other than the compound represented by formula (IV) include cetylpyridinium ion, N-dodecylpyridinium ion, and N-benzyl-2-methylpyridinium ion. , N,N,N,N',N',N'-hexamethyl-1,5-pentane diammonium ion and N,N,N,N',N',N'-hexamethyl-1 ,5-hexanediammonium ion, etc.

The quaternary ammonium salt may also be an intramolecular salt containing carboxylate ions or sulfonate ions in the molecule.

The quaternary ammonium salt is preferably a compound represented by formula (IV), more preferably a compound represented by formula (IV) in which R ⁴¹ to R ⁴⁴ are independently alkyl groups having 1 to 24 carbon atoms, and further preferably In the compound represented by formula (IV), R ⁴¹ to R ⁴⁴ are each independently an alkyl group having 1 to 6 carbon atoms. As the quaternary ammonium salt, more preferred are tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium salicylate, tetrabutylammonium nitrate, tetrabutylammonium hydrogen sulfate, and tetrabutylammonium trifluoromethanesulfonate. Butylammonium, p-nitrophenoxytetrabutylammonium and 3-[dimethyl(tetradecyl)ammonium]propane-1-sulfonate.

〔2〕Fourth grade phosphonium salt

Examples of quaternary phosphonium salts include compounds represented by formula (V).

[In formula (V), R ⁵¹ to R ⁵⁴ each independently represent a alkyl group having 1 to 24 carbon atoms.

Y ^y- represents an anion with y valence.

y represents an integer from 1 to 3].

Examples of the alkyl group having 1 to 24 carbon atoms in R ⁵¹ to R ⁵⁴ include an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, a cycloalkenyl group having 3 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, and an aralkyl group having 7 to 24 carbon atoms. Preferred examples include an alkyl group having 1 to 24 carbon atoms and an aryl group having 6 to 24 carbon atoms.

Examples of the quaternary phosphonium ion in formula (V) include: tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tri-n-octylethylphosphonium ion, hexadecyltriethylphosphonium ion, and Hexaalkyltri-n-butylphosphonium ion, n-butyltriphenylphosphonium ion, n-pentyltriphenylphosphonium ion, methyltriphenylphosphonium ion, benzyltriphenylphosphonium ion and tetraphenylphosphonium ion wait.

Examples of Y ^y- in formula (V) include the same anions as Y ^z- in formula (IV), and preferably are halide ions.

As the quaternary phosphonium salt, tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride and tetra-n-butylphosphonium acetate are preferred.

[3] Grade III cobalt salt

Examples of the tertiary sulfonium salt include compounds represented by formula (VI).

[In formula (VI), R ⁶¹ to R ⁶³ independently represent a hydrocarbon group having 1 to 24 carbon atoms.

Y ^x- represents an anion with x valence.

x represents an integer from 1 to 3].

Examples of the hydrocarbon group in R ⁶¹ to R ⁶³ include alkyl groups having 1 to 24 carbon atoms, cycloalkyl groups having 3 to 24 carbon atoms, alkenyl groups having 2 to 24 carbon atoms, and cycloalkenyl groups having 3 to 24 carbon atoms. Preferable examples of the aryl group having 6 to 24 carbon atoms and the aralkyl group having 7 to 24 carbon atoms include an alkyl group having 1 to 24 carbon atoms and an aryl group having 6 to 24 carbon atoms.

Examples of the tertiary sulfonium ion in formula (VI) include: di-n-butylmethylsulfonium ion, tri-n-butylmethylsulfonium ion, dihexylmethylsulfonium ion, dicyclohexylmethylsulfonium ion and dodecane Methyl ethyl sulfonium ion, etc.

As Y ^x- in formula (VI), the same anions as Y ^z- in formula (IV) can be cited, and halide ions are preferred.

As the tertiary sulfonium salt, di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate and dodecylmethylethylsulfonium chloride are preferred.

The first additive is preferably a quaternary ammonium salt.

Relative to 100 parts by mass of resin (A), the content of the first additive is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 1 Parts by mass ~7 parts by mass. If the content of the first additive is within the above range, the solvent resistance of the cured film formed of the curable resin composition containing the first additive tends to further improve, which is preferable.

<Second additive>

The second additive is at least one compound selected from the group consisting of epoxy compounds and five-membered ring carbonate compounds.

〔1〕Epoxy compound

Epoxy compounds are compounds that have one or more, preferably two or more, cyclopropyl oxy groups in one molecule.

The epoxy compound in the present invention preferably has a weight average molecular weight of less than 1,000. The epoxy compound is a compound having preferably 10 or less oxanyl groups, more preferably 6 or less oxanyl groups.

In the curable resin composition of the present invention, the epoxy compounds shown below are suitably used as the second additive.

[2] Five-membered ring carbonate compounds

The five-membered ring carbonate compound has at least one five-membered ring carbonate structure in the molecule, preferably two or more five-membered ring carbonate structures.

Examples of five-membered ring carbonate compounds include: 1,3-dioxolane-2-one, 4-butyl-1,3-dioxolane-2-one, 4,5- Dimethyl-1,3-dioxolane-2-one, allylsuccinic anhydride, 4-(meth)acrylyloxymethyl-1,3-dioxolane-2 -one, 4-allyloxymethyl-1,3-dioxolane-2-one and 4-vinyloxymethyl-1,3-dioxolane-2- Ketones etc.

The second additive is preferably an epoxy compound.

The content of the second additive is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass relative to 100 parts by mass of the resin (A). If the content of the second additive is within the above range, the solvent resistance of the cured film formed from the curable resin composition containing the second additive tends to further improve, which is preferable.

The weight ratio of the first additive to the second additive is preferably 1:1 to 1:20 for the first additive: the second additive, more preferably 1:1 to 1:10, and even more preferably 1:1 to 1:5.

<Polymerizable compound (C)>

The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by active radicals generated from the polymerization initiator (D) due to light irradiation or the like. Examples thereof include those having an ethylenically unsaturated bond. compound, preferably a (meth)acrylic acid compound.

As compounds having one ethylenically unsaturated bond, there can be listed compounds which are the same as the monomers from which each constituent unit constituting the resin (A) is derived, etc.

Examples of compounds having two ethylenically unsaturated bonds include: 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,6-hexanediol Alcohol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate Meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, ethylene oxide modified bisphenol A Di(meth)acrylate, propylene oxide modified neopentyl glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate and 3-methylpentanediol Di(meth)acrylate, etc.

Examples of compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and tris(2-hydroxyethyl)isocyanurate. Acid ester tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate Meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, the reactant of pentaerythritol tri(meth)acrylate and acid anhydride, The reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, the reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride, caprolactone modified trimethylolpropane tri(meth)acrylate, hexanol Lactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified tri(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(methyl) Acrylates, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, caprolactone Ester-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol Octa(meth)acrylate, the reactant of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, the reactant of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, and caprolactone Modified reaction products of tripentaerythritol hepta(meth)acrylate and acid anhydride, etc.

As a compound having an ethylenically unsaturated bond, a compound having three or more ethylenically unsaturated bonds is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred. These compounds may be used individually or in combination of 2 or more types.

When the curable resin composition of the present invention contains the polymerizable compound (C), its content is preferably 20 parts by mass based on 100 parts by mass of the resin (A). Parts by mass to 200 parts by mass, more preferably 30 parts by mass to 150 parts by mass. When the content of the polymerizable compound (C) is within the above range, the strength, smoothness and reliability of the cured film obtained by curing the curable resin composition containing the polymerizable compound (C) tend to become good, which is preferable.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and start the polymerization of the polymerizable compound (C), and a known polymerization initiator can be used.

Preferable examples of the polymerization initiator (D) include at least one selected from the group consisting of O-acyl oxime compounds, phenylalkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, and biimidazole compounds. As a polymerization initiator, more preferably, a polymerization initiator containing an O-acyl oxime compound can be mentioned.

When the polymerization initiator (D) is these polymerization initiators, the curable resin composition containing these polymerization initiators has high sensitivity, and the cured film formed of the curable resin composition containing them has transmission in the visible light region. rate tends to increase.

The O-acyl oxime compound is a compound having a structure represented by formula (D1). In the following, * indicates a bonding key.

As O-acyl oxime compounds, there can be mentioned: N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, N-acetyloxy-1-[9 -ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolatocyclopentylmethyloxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (both manufactured by BASF), N-1919, NCI-831 and NCI-930 (manufactured by ADEKA) can also be used.

The phenylalkyl ketone compound is a compound having a structure represented by formula (D2-1) or a structure represented by formula (D2-2). In these structures, the benzene ring may have a substituent.

Examples of the compound having the structure represented by formula (D2-1) include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (manufactured by BASF Corporation) can also be used. A polymerization initiator having a group capable of causing chain transfer described in Japanese Patent Publication No. 2002-544205 can also be used. Examples of compounds having a structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzoyl dimethyl ketal. In terms of sensitivity, compounds having a structure represented by formula (D2-1) are preferred as phenylalkyl ketone compounds.

Examples of the triazine compound include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, Methyl)-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)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine .

As the acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide and the like can be cited. Commercially available products such as Irgacure 819 (manufactured by BASF Corporation, Japan) can also be used.

Examples of biimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis( 2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, see Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.) and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, see Japanese Patent Publication No. 7-10913, etc.).

Furthermore, as the polymerization initiator (D), there can be listed: benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzoyl, methyl phenylglyoxylate, and titaniumocene compounds. These can be used in combination with the polymerization initiator aid (H) (especially amines) described later.

When the curable resin composition of the present invention contains the polymerization initiator (D), its content is preferably 0.1 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). parts to 30 parts by mass, more preferably 0.5 parts to 20 parts by mass, and more preferably 5 parts to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the cured film formed from the curable resin composition containing the polymerization initiator (D) tends to have more excellent solvent resistance and high visible light transmittance.

<Polymerization initiation aid (H)>

The polymerization initiator aid (H) is a compound or sensitizer used together with the polymerization initiator (D) to promote the polymerization of the polymerizable compound (C) that has started to polymerize by the polymerization initiator (D).

Examples of the polymerization starting aid (H) include a thiazoline compound, an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the thiazoline compound include compounds represented by formula (H1-1) to formula (H1-3), compounds described in Japanese Patent Application Laid-Open No. 2008-65319, and the like.

Examples of the amine compound include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis (ethylmethylamino)benzophenone and the like, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of alkoxyanthracene compounds include: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

As thiothione compounds, there can be listed: 2-isopropylthiothione, 4-isopropylthiothione, 2,4-diethylthiothione, 2,4-dichlorothiothione, 1-chloro-4-propoxythiothione, etc.

As carboxylic acid compounds, there can be listed: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

When the curable resin composition of the present invention contains the polymerization starting aid (H), its content is preferably 0.1 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). Parts by mass to 30 parts by mass, preferably 0.2 parts by mass to 10 parts by mass. When the amount of the polymerization initiation aid (H) is within the above range, when a pattern is formed from the curable resin composition containing it, the sensitivity tends to become higher.

<Leveling agent (B)>

Examples of the leveling agent (B) include silicone-based surfactants (which do not contain fluorine atoms), fluorine-based surfactants (which do not contain silicon atoms), silicone-based surfactants having fluorine atoms, and the like. These may have a polymerizable group in a side chain.

As silicone-based surfactants (which do not contain fluorine atoms), surfactants having siloxane bonds in the molecule can be listed. Specifically, they include: Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name; Toray Dow Corning Corning (manufactured by), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.

As the fluorine-based surfactant (which does not contain silicon atoms), there can be cited surfactants having fluorine-carbon chains in the molecule, etc. Specifically, there can be cited: Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS -718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratories Co., Ltd.), etc.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (DEX) manufacturing), etc.

As the leveling agent (B), a fluorine-based surfactant (containing no silicon atoms) is preferred.

When the leveling agent (B) is contained, the content rate is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more with respect to the solid content in the curable resin composition. 0.1 mass% or less, more preferably 0.005 mass% or more and 0.1 mass% or less.

<Solvent (E)>

The curable resin composition of the present invention may contain a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. For example, ester solvents (solvents that contain -COO- but not -O- in the molecule), ether solvents (solvents that contain -O- but do not contain -COO- in the molecule), ether ester solvents (solvents that do not contain -COO- in the molecule), Solvents that contain -COO- and -O-), ketone solvents (solvents that contain -CO- and do not contain -COO- in the molecule), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO - and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl styrene, etc.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenylethyl ether and methyl anisole, etc.

As ether ester solvents, there can be listed: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, etc.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

As alcohol solvents, there are: methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerol, etc.

As aromatic hydrocarbon solvents, we can cite: benzene, toluene, xylene and mesitylene, etc.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the solvents, in terms of coating properties and drying properties, organic solvents having a boiling point of 100°C to 200°C at 1 atm are preferred. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, and cyclohexane are preferred. ketone, methoxybutanol and methoxybutyl acetate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxy butanol and methoxy butyl acetate.

The content of the solvent (E) in the curable resin composition of the present invention is preferably 60% by mass to 95% by mass, and more preferably 70% by mass to 95% by mass, relative to the total amount of the curable resin composition. In other words, the solid content of the curable resin composition of the present invention is preferably 5% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass. If the content of the solvent (E) is within the above range, the coating properties of the curable resin composition tend to be improved.

<Color(K)>

The curable resin composition of the present invention may also contain a colorant (K). Examples of the colorant (K) include dyes and/or pigments. These may be used alone or in combination of two or more colorants. In this case, the colorant may be a combination of only dyes, only pigments, or a combination of dyes and pigments.

Dyes can be used without particular limitation and known dyes can be listed, such as solvent dyes, acid dyes, direct dyes, mordant dyes, etc. As dyes, for example, compounds with hues other than pigments classified in the Color Index (published by The Society of Dyers and Colourists) or known dyes listed in the Dyeing Notes (Shikisensha Co., Ltd.) can be listed. In addition, based on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthone dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azoformine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes can be listed.

Specifically, they include: C.I. Solvent Yellow 4 (hereinafter, the number is omitted), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange Orange) 2, 7, 11, 15, 26, 56, 77, 86; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green C.I. solvent dyes such as Green)1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C.I. Acid Yellow (Acid Yellow)1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160 、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251； C.I. Acid Red (Acid Red)1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 19 5, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange Orange) 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue Blue)1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 1 27, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340; C.I. Acid Green (Acid Green C.I. Acid Dyes: C.I. Green (1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109, etc.; C.I. Direct Yellow (Direct Yellow) (2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; C.I. Direct Red (Direct Red)79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange (Direct Orange)26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Purple (Direct Violet)47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104; C.I. Direct Blue (Direct 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 1 70, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green Green) 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other C.I. direct dyes; Disperse Yellow 51, 54, 76; Disperse Violet 26, 27; Disperse Blue 1, 14, 56, 60 and other C.I. disperse dyes; Basic Red 1, 10; Basic Blue 1, 2 Blue) 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1 and other C.I. Alkaline dyes; C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36 and other C.I. Reactive dyes; C.I. Mordant Yellow (Mordant Yellow) C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange ... 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Blue Blue) 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other C.I. mordant dyes; C.I. Vat Green 1 and other C.I. Vat dyes, etc.

In addition, dyes described in Japanese Patent Publication No. 2010-32999, Japanese Patent Publication No. 4492760, Japanese Patent Publication No. 2013-50693, and Japanese Patent Publication No. 2013-178478 can be cited.

These dyes can be appropriately selected according to the desired spectral spectrum of the color filter.

Examples of the pigment include organic pigments and inorganic pigments, and examples include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

Examples of pigments include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, etc.; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; and red pigments such as C.I. Pigment Red. Red pigments such as 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments such as C.I. Pigment Green 7, 36, 58, 59, etc.; brown pigments such as C.I. Pigment Brown 23, 25, etc.; black pigments such as C.I. Pigment Black 1, 7, etc., etc.

Among them, it is preferred to contain at least one pigment selected from C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, 254, C.I. Pigment Purple 23, C.I. Pigment Blue 15:6 and C.I. Pigment Green 7, 36, 58, 59. These pigments can be used alone or in combination of two or more.

As the pigment, rosin treatment, surface treatment using pigment derivatives with acidic or alkaline groups, grafting treatment on the pigment surface using polymer compounds, micronization treatment using sulfuric acid micronization method, cleaning treatment using organic solvents or water to remove impurities, removal treatment of ionic impurities using ion exchange method, etc. can also be performed as needed.

As the pigment dispersant, for example, cationic, anionic, nonionic, amphoteric, polyester, polyamide, acrylic surfactants and the like can be listed. These can be used alone or in combination of two or more. Specifically, the trade names that can be listed are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-chemie Co., Ltd.), etc.

When a pigment dispersant is used, the usage amount is preferably 1 part by mass or more and 100 parts by mass or less based on 100 parts by mass of the total amount of pigment, and more preferably 100 parts by mass or less. 5 parts by mass or more and 50 parts by mass or less. When the usage amount of the pigment dispersant is within the above range, a pigment dispersion liquid with a uniform dispersion state tends to be obtained.

When the curable resin composition of the present invention contains a colorant (K), its content relative to the total amount of solid components is preferably 5% to 70% by mass, more preferably 8% to 65% by mass, and further preferably 10% to 60% by mass. If the content of the colorant (K) is within the above range, the target chromaticity can be prepared.

<Other ingredients>

The curable resin composition of the present invention may also contain fillers, other polymer compounds, antioxidants, ultraviolet absorbers, chain transfer agents, adhesion promoters and other additives known in the art as needed.

When the curable resin composition of the present invention does not contain a colorant, it is filled in a quartz cell with an optical path length of 1 cm, and the transmittance is measured using a spectrophotometer under the conditions of a measurement wavelength of 400 nm to 700 nm. The average The transmittance is preferably 70% or more, more preferably 80% or more.

When the curable resin composition of the present invention does not contain a colorant, the average transmittance of the cured film formed from the composition is preferably 90% or more, more preferably 95% or more. This average transmittance is the average when a film with a thickness of 2 μm after heat curing (100°C to 250°C, 5 minutes to 3 hours) is measured using a spectrophotometer under the conditions of a measurement wavelength of 400nm to 700nm. value. Thereby, a cured film excellent in transparency in the visible light range can be provided.

[Method for manufacturing curable resin composition]

The curable resin composition of the present invention can be obtained by converting the resin into (A), the first additive and the second additive, and if necessary, a solvent (E), a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation aid (H), and a leveling agent (B), colorant (K) and other components are mixed and produced. After mixing, it is preferable to filter using a filter with a pore size of about 0.05 μm to 0.5 μm.

[Manufacturing method of hardened film]

The cured film of the present invention can be produced by applying the curable resin composition of the present invention on a substrate, drying and then heating. More specifically, the manufacturing method of the cured film of the present invention includes the following steps (1) to (3).

Step (1): the step of applying the curable resin composition of the present invention to a substrate; step (2): drying the applied curable resin composition under reduced pressure and/or heating to form a composition layer. Step; step (3): the step of heating the composition layer.

In addition, when the curable resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D), a cured film having a pattern can be produced by performing the following steps.

Step (1): coating the curable resin composition of the present invention on a substrate; Step (2): drying the coated curable resin composition under reduced pressure and/or heat drying to form a composition layer; Step (2a): exposing the composition layer through a photomask; Step (2b): developing the exposed composition layer; Step (3a): heating the developed composition layer.

Step (1) is a step of coating the curable resin composition of the present invention on a substrate (base substrate). As the substrate, glass, metal, plastic, etc. can be listed, and a color filter, an insulating film, a conductive film and/or a driving circuit can also be formed on the substrate. The coating on the substrate is preferably carried out using a coating device such as a rotary coater, a slit and rotary coater, a slit coater, an inkjet, a roller coater, an immersion coater, etc.

Step (2) is a step of drying the applied curable resin composition under reduced pressure and/or heating to form a composition layer. By performing this step, volatile components such as solvents in the curable resin composition are removed. Reduced pressure drying is preferably performed at a pressure of 50 Pa to 150 Pa and a temperature range of 20°C to 25°C. Heating drying (prebaking) may also be performed before or after reduced pressure drying. Heating drying is usually performed using heating devices such as ovens and hot plates. The temperature for heating and drying is preferably 30°C to 120°C, and more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

Step (3) is a step of heating the component layer (post-baking). Heating is usually performed using a heating device such as an oven or a heating plate. The heating temperature is preferably 80°C to 220°C, more preferably 90°C to 200°C, and further preferably 90°C to 150°C. The heating time is preferably 1 minute to 120 minutes, and more preferably 3 minutes to 60 minutes. By heating under such conditions, a cured film with excellent solvent resistance can be obtained without reducing the characteristics of the substrate, etc.

Step (2a) is a step of exposing the composition layer formed in step (2) through a light mask. The photomask having a light-shielding portion formed corresponding to the portion where the composition layer is to be removed is used. 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 in exposure, it is preferable to generate 250nm~450nm The wavelength of the light source. For example, for light less than 350nm, a filter that cuts off the wavelength range can be used to cut off, or for light near 436nm, 408nm, and 365nm, a bandpass filter that extracts these wavelength ranges can be used for selective extraction. Examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like. In order to uniformly illuminate the entire exposure surface with parallel light or to accurately align the mask and the composition layer, it is preferred to use exposure devices such as a mask aligner and a stepper.

Step (2b) is a step of developing the exposed component layer. The exposed component layer is brought into contact with a developer to perform development, and the unexposed portion of the component layer is dissolved in the developer and removed, thereby forming a component layer with a pattern on the substrate. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, etc. is preferred. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass. Furthermore, the developer may also contain a surfactant. The developing method may be any one of a coating method, an immersion method, and a spray method. Furthermore, the substrate can be tilted to any angle during development. After development, it is better to wash with water.

Step (3a) is a step of heating the developed component layer. By heating in the same manner as step (3), the component layer with the pattern is hardened, thereby forming a hardened film with the pattern on the substrate.

According to the curable resin composition of the present invention, even when cured at low temperatures such as 140°C to 150°C, a cured film having excellent solvent resistance can be produced. The cured film is useful as an optical spacer, outer coating, or interlayer insulating film used in a display device. In addition, when the curable resin composition of the present invention contains a colorant, it is useful as a color filter used in a display device such as a liquid crystal display device, an organic electroluminescence (EL) device, an electronic paper, and a solid-state imaging element.

[Example]

Hereinafter, the present invention will be described in more detail by enumerating examples. "%" and "parts" in the examples refer to mass % and mass parts unless otherwise specified.

(Synthesis Example 1: Synthesis of copolymer (a1))

Add 80 parts of propylene glycol monomethyl ether to a flask equipped with a stirring wing, a reflux cooling tube, a thermometer and a dropping funnel, and heat it to 90°C. Mix 41.3 parts of vinyltoluene, 26.6 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 27.1 parts of methacrylic acid, 5 parts of azobis(isobutyronitrile), and propylene glycol. The solution obtained by adding 30 parts of monomethyl ether was continuously added dropwise into the flask using a dropping funnel. The temperature in the flask was maintained at 90±1°C while the mixed solution was being dropped, and the dropwise addition was completed after 3 hours. After the dropwise addition is completed, the temperature in the flask is maintained at 90±1°C for 6 hours. After the reaction, the reaction liquid was cooled to below 40°C, and 0.12 parts of 4-methoxyphenol, 22.6 parts of 3,4-epoxycyclohexyl methacrylate, 4.7 parts of triphenylphosphine, and 90 parts of propylene glycol monomethyl ether were added. parts, after raising the temperature in the flask to 110°C, an addition reaction was performed at the temperature in the flask of 110±1°C, thereby obtaining a copolymer (a1) solution with a solid content of 36.5%. The weight average molecular weight (Mw) of the copolymer (a1) is 16,500, the dispersion degree is 2.4, and the acid value in terms of solid content is 92 mg-KOH/g. Copolymer (a1) has the following structural units.

(Synthesis Example 2: Synthesis of Copolymer (a2))

In a flask equipped with a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel, 70 parts of propylene glycol monomethyl ether were added and heated to 90°C. A solution obtained by mixing 52.6 parts of dicyclopentanyl methacrylate, 20.7 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 26.7 parts of methacrylic acid, 5 parts of azobis(isobutyronitrile), and 30 parts of propylene glycol monomethyl ether was continuously dropped into the flask using a dropping funnel. The temperature in the flask was maintained at 90±1°C during the dropwise addition of the mixed solution, and the dropwise addition was completed after 3 hours. After the dropwise addition was completed, the temperature in the flask was maintained at 90±1°C for 6 hours. After the reaction, the reaction liquid was cooled to below 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxyhexyl methacrylate, 4.7 parts of triphenylphosphine, and 85 parts of propylene glycol monomethyl ether were added. After the temperature in the flask was raised to 110°C, an addition reaction was carried out at a temperature in the flask of 110±1°C to obtain a copolymer (a2) solution with a solid content of 37.9%. The weight average molecular weight (Mw) of the obtained copolymer (a2) was 14,300, the dispersion was 2.4, and the acid value converted to solid content was 103 mg-KOH/g. The copolymer (a2) has the following constituent units.

(Synthesis Example 3: Synthesis of copolymer (a3))

In a flask equipped with a stirring blade, a reflux cooling tube, a thermometer, and a dropping funnel, 70 parts of propylene glycol monomethyl ether were added and heated to 90°C. A solution obtained by mixing 44.6 parts of methyl methacrylate, 28.6 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 26.8 parts of methacrylic acid, 5 parts of azobis(isobutyronitrile), and 30 parts of propylene glycol monomethyl ether was continuously dripped into the flask using a dropping funnel. The temperature in the flask was maintained at 90±1°C during the dripping of the mixed solution, and the dripping was completed in 3 hours. After the dripping was completed, the temperature in the flask was maintained at 90±1°C for 6 hours. After the reaction, the reaction liquid was cooled to below 40°C, and 0.12 parts of 4-methoxyphenol, 24.4 parts of 3,4-epoxyhexyl methacrylate, 5 parts of triphenylphosphine, and 95 parts of propylene glycol monomethyl ether were added. After the temperature in the flask was raised to 110°C, an addition reaction was carried out at a temperature in the flask of 110±1°C to obtain a copolymer (a3) solution with a solid content of 38.5%. The weight average molecular weight (Mw) of the obtained copolymer (a3) was 15,800, the dispersion was 2.4, and the acid value converted to solid content was 80 mg-KOH/g. The copolymer (a3) has the following constituent units.

(Synthesis Example 4: Synthesis of Resin (a))

100 parts of propylene glycol monomethyl acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred and heated to 120°C while replacing nitrogen. Next, 43 parts of methyl methacrylate, 25 parts of methacrylic acid, and 0.68 parts of tert-butylperoxy-2-ethylhexanoate (Perbutyl O; manufactured by NOF Co., Ltd.) were mixed. The obtained liquid was added dropwise from the dropping funnel to the flask over 2 hours, and further stirred at 120° C. for 2 hours to obtain a copolymer. Secondly, the air in the flask was replaced, and 10 parts of glycidyl methacrylate, 0.44 parts of triphenylphosphine and 0.08 parts of methylhydroquinone were put into the copolymer solution, and the reaction was continued at 120°C. The reaction was completed when the acid value of the solid content reached 100 mg-KOH/g. 50 parts of propylene glycol monomethyl acetate was added thereto to obtain a resin (a) solution with a solid content of 40%. The weight average molecular weight (Mw) of the resin (a) is 30,000, the dispersion degree is 2.5, and the acid value in terms of solid content is 100 mg-KOH/g. Resin (a) has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Tube string temperature: 40℃

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0mL/min

Solid content concentration of the test liquid: 0.001 mass%~0.01 mass%

Injection volume: 50μL

Detector: refractive index (RI)

Standard materials for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the obtained polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) was defined as the degree of dispersion.

(Synthesis Example 5: Synthesis of a compound represented by formula (A-IV))

20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (produced by Wako Junyaku Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours. After the resulting reaction solution was cooled to room temperature, it was added to a mixture of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, resulting in crystal precipitation. After the precipitated crystals were obtained in the form of suction-filtered residues, they were dried to obtain the compound represented by formula (A-IV).

Identification of compounds represented by formula (A-IV)

(Mass analysis) Ionization mode = ESI+: m/z = [M+H] ⁺ 659.3

Exact Mass: 658.3

[Example 1 to Example 19, Example 21 to Example 23, Comparative Example 1 and Comparative Example 2]

<Preparation of hardening resin composition>

The components shown in Table 1 are contained in the proportions shown in Table 1, and the solvent (E) of each curable resin composition is a mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (the mixing ratio is 1:1 in terms of mass ratio), and the curable resin composition is obtained by mixing in a manner to obtain the solid component concentration shown in Table 1.

In Table 1, the number of parts of each component represents the mass part converted into solid content.

[Table 1]

Copolymer (a1): Copolymer obtained by Synthesis Example 1

Copolymer (a2): Copolymer obtained by Synthesis Example 2

Copolymer (a3): Copolymer obtained by Synthesis Example 3

Resin (a): Copolymer obtained by Synthesis Example 4

(x1): Tetrabutylammonium chloride

(x2): p-Nitrophenoxytetrabutylammonium

(x3): Tetrabutylammonium bromide

(x4): Tetrabutylammonium salicylate

(x5): Tetrabutylammonium nitrate

(x6): Tetrabutylammonium trifluoromethanesulfonate

(x7): Tetrabutylammonium hydrogen sulfate

(x8): 3-[Dimethyl(tetradecyl)ammonium]propane-1-sulfonate (produced by Tokyo Chemical Industry Co., Ltd.)

(y1): Compound represented by the following formula (ED-529; manufactured by Aidico Co., Ltd.)

(y2): Compound represented by the following formula (DA-MGIC; manufactured by Shikoku Chemical Industries, Ltd.)

(y3): A compound represented by the following formula (MA-DGIC; manufactured by Shikoku Chemical Industries, Ltd.)

(y4): A compound represented by the following formula (TEPIC (registered trademark); manufactured by Nissan Chemical Industries, Ltd.)

(y5): Compound represented by the following formula (S-184; manufactured by SYNASIA)

(y6): Compound represented by the following formula (TG-G; manufactured by Shikoku Chemical Industries, Ltd.)

(y7): A compound represented by the following formula (S-500; manufactured by Synasia Corporation)

(y8): A compound represented by the following formula (S-186; manufactured by Synasia Corporation)

(y9): Compound represented by the following formula (S-400; manufactured by Shinnashi Corporation)

(f1): Fluorine-based leveling agent (Megafac (registered trademark) F554; manufactured by DIC Corporation)

<Preparation of hardened film 1>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Company) was washed with neutral detergent, water and isopropyl alcohol in sequence and then dried. On this substrate, the curable resin composition was spin-coated so that the film thickness after baking would be 1.5 μm. Secondly, use a vacuum dryer (vacuum chamber dryer (VCD); manufactured by Microtech Co., Ltd.), set the rotary pump to a rotation speed of 1000 rpm, and a booster pump to ), under the conditions of 700 rpm and normal temperature of 25°C, dry under reduced pressure until the degree of reduced pressure reaches 66Pa. Thereafter, the cured film was obtained by baking at 140° C. for 3 minutes on a hot plate.

<Evaluation of solvent resistance>

The obtained cured film was immersed in propylene glycol monomethyl ether acetate at 23°C for 3 minutes and then thoroughly washed with water. The film thickness was measured before immersion and after water washing (the film thickness before immersion was set as t1, and the film thickness after water washing was set as t2), and the ratio of the film thickness after water washing to the film thickness before immersion was calculated (t2/t1). In addition, a film thickness measuring device (DEKTAK XT; manufactured by Nippon Vacuum Technology Co., Ltd.) was used for the film thickness measurement. The results are shown in Table 1.

[Example 20]

<Preparation of Curable Resin Composition>

Mix, use a bead mill to fully disperse the pigment, and then,

Mix to obtain a hardening resin composition.

<Production of hardened film 2>

The curable resin composition was coated on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a composition layer. . After leaving it to cool, the distance between the substrate on which the composition layer was formed and the quartz glass mask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to expose the substrate at 80 mJ in the atmospheric environment. /cm ² of exposure (365nm reference) for light irradiation. As a photomask, a photomask in which a 1:1 line and space pattern of 100 μm was formed was used. The composition layer after light irradiation was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C for 60 seconds. After washing with water, it was developed on a hot plate at 150°C. °C for 5 minutes to obtain a cured film with a pattern.

Regarding the cured film prepared from the curable resin composition of Example 20 using the method of preparing the cured film 2, the solvent resistance was evaluated by the same method as described above, and the result (t2/t1) was 1.

According to the present invention, it is possible to provide a curable resin composition capable of forming a cured film having excellent solvent resistance, and the cured film is suitable for display devices and the like.

Claims (3)

A curable resin composition comprising: a resin (A), wherein the resin (A) is a copolymer containing a constituent unit (Aa) having an α,β-unsaturated carbonyl group, a constituent unit (Ab) having an active methylene group or an active methine group, and a constituent unit (Ac1) having an acid group; and a quaternary ammonium salt and an epoxy compound. The curable resin composition as described in claim 1, wherein the epoxy compound is an epoxy compound having at least two oxiryl groups in one molecule. A cured film formed of the curable resin composition described in the first or second claim of the patent application.