JP7180994B2 - Curable resin composition and cured film - Google Patents

Description

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

Examples of Patent Document 1 include a composition containing as a resin component a reaction product obtained by polymerizing methyl methacrylate, ethyl methacrylate and methacrylic acid and then reacting glycidyl methacrylate, and curing the composition at 230°C. The resulting cured films are described.

JP-A-3-172301

A curable resin composition that has good solvent resistance in the cured film obtained even when the heating temperature in the curing step is lowered, for example, to 140 ° C. to 150 ° C., compared to the conventionally known composition. offer.

The present invention includes the following.
[1] containing a resin (A), a first additive and a second additive,
The resin (A) is a copolymer containing a structural unit (Aa) having an α,β-unsaturated carbonyl group and a structural unit (Ab) having an active methylene group or an active methine group,
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 curable resin composition, wherein the second additive is at least one compound selected from the group consisting of epoxy compounds and five-membered ring carbonate compounds.
[2] The curable resin composition of [1], wherein the first additive is a quaternary ammonium salt and the second additive is an epoxy compound.
[3] The curable resin composition according to [1] or [2], wherein the epoxy compound is an epoxy compound having at least two oxiranyl groups in one molecule.
[4] A cured film formed from the curable resin composition according to any one of [1] to [3].

According to the curable resin composition of the present invention, a cured film having excellent solvent resistance can be formed even at a low curing temperature.

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

[Curable resin composition]
The curable resin composition of the present invention comprises a resin (hereinafter referred to as resin (A)), a first additive (hereinafter referred to as first additive (X)) and a second additive (hereinafter referred to as second 2 additive (Y)). The curable resin composition of the present invention may further contain a solvent (hereinafter referred to as solvent (E)).
The resin (A) comprises a structural unit having an α,β-unsaturated carbonyl group (hereinafter referred to as a structural unit (Aa)) and a structural unit having an active methylene group or an active methine group (hereinafter referred to as a structural unit (Ab) It is a copolymer containing.
The first additive (X) is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts and tertiary sulfonium salts.
The second additive (Y) is at least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds.
By allowing the resin (A) to coexist with the first additive (X) and the second additive (Y), the resulting cured film has excellent solvent resistance.

The curable resin composition of the present invention may contain a polymerizable compound (hereinafter referred to as polymerizable compound (C)). When the polymerizable compound (C) is contained, it is preferable to also contain a polymerization initiator (hereinafter referred to as polymerization initiator (D)). The curable resin composition of the present invention also contains other components such as a polymerization initiation aid (hereinafter referred to as polymerization initiation aid (H)) and a leveling agent (hereinafter referred to as a leveling agent (B). ), coloring agent (hereinafter referred to as coloring agent (K)), and the like.

<Resin (A)>
Resin (A) has a structural unit (Aa) and a structural unit (Ab). The resin (A) may further contain other structural units (hereinafter referred to as structural units (Ac)). The resin (A) may contain two or more kinds of each of the structural units (Aa) and the structural units (Ab).

Resin (A) is preferably an alkali-soluble resin. Alkali solubility refers to the property of dissolving in a developer that is an aqueous solution of an alkaline compound. The resin (A) preferably contains a structural unit having an acid group (hereinafter referred to as a structural unit (Ac1)) as a structural unit (Ac). The resin (A) may contain a structural unit other than the structural unit (Ac1) (hereinafter referred to as structural unit (Ac2)) as the structural unit (Ac). Each structural unit will be described in detail below.
In this specification, "(meth)acrylic acid" represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth)acryloyl" and "(meth)acrylate" have the same meaning.

[1] Structural unit (Aa)
In the present specification, the α,β-unsaturated carbonyl group is a structure represented by -CO-CX=CX- (X independently represents an optional substituent), preferably -CO-CX =CH-. X includes 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, and preferably a hydrogen atom or a methyl group. .
The structural unit (Aa) is, for example, a structural unit having a carboxy group (hereinafter referred to as a structural unit (Aa')) and a compound having an α,β-unsaturated carbonyl group (hereinafter referred to as a carboxylic acid-reactive compound ) is added. Examples of carboxylic acid-reactive compounds include compounds having an oxiranyl group and an α,β-unsaturated carbonyl group (hereinafter referred to as compound (Aa'')). Examples of the structural unit (Aa') include structural units having a carboxy group among the structural units (Ac1) described later.
Alternatively, it can be obtained by reacting a structural unit having an oxiranyl group with (meth)acrylic acid.

The compound (Aa'') includes a compound having an epoxidized linear or branched unsaturated aliphatic hydrocarbon structure and an α,β-unsaturated carbonyl group (hereinafter referred to as compound (Aa'' -1).), and a compound having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized and an α,β-unsaturated carbonyl group (hereinafter referred to as compound (Aa''-2).) is mentioned.

Examples of the compound (Aa''-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl itaconate and the like.
Specific examples of the compound (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 ]decane-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,
5,6-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate,
5,6-epoxytricyclo[5.2.1.0 ^2,6 ]decane-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)cyclohexylmethyl (meth)acrylate,
3-(3,4-epoxycyclohexyl)-9-hydroxy-1,5-dioxaspiro[5,5]undecane-8-yl (meth)acrylate,
3-(3,4-epoxycyclohexyl)-9-hydroxy-2,4-dioxaspiro[5,5]undecane-8-yl (meth)acrylate,
etc. These can be used alone, or can be used in combination of two or more. Among these, glycidyl (meth)acrylate or 3,4-epoxycyclohexylmethyl (meth)acrylate is preferably used.

For example, a structural unit (Aa) obtained by adding 3,4-epoxycyclohexylmethyl (meth)acrylate to a (meth)acrylic acid structural unit is represented by formula (Aa-1).

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

For example, a structural unit (Aa) obtained by adding glycidyl (meth)acrylate to a (meth)acrylic acid structural 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 structural unit (Aa), a structural unit represented by formula (Aa-1) or a structural unit represented by formula (Aa-2) is preferable.

[2] Structural unit (Ab)
A structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene group or an active methine group. A structural unit derived from an unsaturated compound having an active methylene group or an active methine group means a structural unit derived from the unsaturated compound in a copolymer obtained by polymerizing the unsaturated compound as a monomer. A copolymer having such structural units can be obtained by polymerizing an unsaturated compound having an active methylene group or an active methine group as a monomer.

The unsaturated compound having an active methylene group leading to the structural unit (Ab) includes a compound represented by formula (I), and the unsaturated compound having an active methine group is a compound represented by formula (II). is mentioned.

[In formula (I) and formula (II),
R ¹¹ represents a group represented by any one of formulas (1-1) to (1-4).
R ¹² represents a single bond, -X- or -X-O-* (* represents a bond with R ¹³ ).
R ¹³ represents -CO- or -SO ₂ -.
R ¹⁴ represents —CO—R ¹⁵ , —SO ₂ —R ¹⁵ , a cyano group or a nitro group.
X represents a divalent hydrocarbon group having 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 formulas (1-1) to (1-4), R ¹⁶ and R ¹⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms.
R ¹⁷ represents a hydrocarbon group having 1 to 24 carbon atoms, and the methylene group contained in the hydrocarbon group may be replaced with -CO- or -O-. ]

Examples of hydrocarbon groups having 1 to 24 carbon atoms for R ¹⁵ to R ¹⁸ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and hexyl group; and cycloalkyl groups such as cyclohexyl group.
When the methylene group contained in the above hydrocarbon group in R ¹⁷ is replaced with —O— or —CO—, the hydrocarbon group has 2 to 24 carbon atoms. Examples of the group in which the methylene group contained in the hydrocarbon group of the hydrocarbon group having 2 to 24 carbon atoms is replaced with -O- or -CO- include an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a hexyloxy group; cycloalkoxy groups such as cyclohexyloxy group; oxo group-containing hydrocarbon groups such as 2,4-dioxopentyl group, 3,5-dioxohexyl group and 1,3-dioxobutyloxyethyl group;
The divalent hydrocarbon group having 1 to 20 carbon atoms in X includes methylene group, ethylene group, propanediyl group, butanediyl group, hexanediyl group, octanediyl group, decanediyl group, dodecanediyl group and the like. A divalent chain aliphatic hydrocarbon group; a cyclohexanediyl group, a tricyclodecanediyl group, a divalent cycloaliphatic hydrocarbon group having 3 to 20 carbon atoms such as a group represented by the following formula; phenylene divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms such as groups, preferably methylene group or 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 -X-O-* (* represents a bond with R ^13. ), preferably X is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms is.
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.

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

Compounds represented by any of formulas (I-1) to (I-7), formula (I-16), formula (II-1) and formula (II-2) have R ¹¹ represented by formula (1 -1) and R ¹⁶ is a methyl group, but a compound in which the methyl group of R ¹⁶ is replaced with a hydrogen atom can also be mentioned as a compound leading to the structural unit (Ab). can.

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

[In the 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. ]

The alkyl group having 1 to 6 carbon atoms in R ⁴ includes methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n- A hexyl group and the like can be mentioned.
R ⁴ preferably includes a hydrogen atom and a methyl group.
Examples of the compound leading to the structural unit represented by formula (Ab-1) include 2-(1,3-dioxobutyloxy)ethyl (meth)acrylate [compound represented by formula (I-1)]. mentioned.

[3] Structural unit (Ac1)
A structural unit (Ac1) is a structural unit derived from an unsaturated compound having an acid group. A carboxy group, a phenolic hydroxy group, a sulfo group, etc. are mentioned as an acid group. An unsaturated compound having two or more carboxy groups may be an acid anhydride. A structural unit derived from an unsaturated compound having an acid group means a structural unit derived from the unsaturated compound in a copolymer obtained by polymerizing the unsaturated compound as a monomer. A copolymer having such structural units can be obtained by polymerizing an unsaturated compound having an acid group as a monomer. It can also be obtained by adding an acid anhydride to a copolymer having a structural unit having a hydroxy group.
The resin (A) preferably has a structural 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 acid 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-methyl Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1] unsaturated monocarboxylic acids such as hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, α-(hydroxymethyl)(meth)acrylic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (hymic acid anhydride);
Divalent or higher polyvalent carboxylic acid unsaturated mono[(meth)acryloyloxyalkyl] esters such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;
etc.

Among these, (meth)acrylic acid and maleic anhydride are preferable because they are excellent in copolymerization reactivity and alkali solubility of the copolymer. These are used singly or in combination.

[4] Structural unit (Ac2)
Structural unit (Ac2) is a structural unit different from structural units (Aa), (Ab) and (Ac1). Structural unit (Ac2) is derived from a monomer polymerizable with a monomer leading to other structural units (eg, structural unit (Aa), (Ab) or (Ac1)). Specific examples of such monomers include:
methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (commonly known as dicyclopentanyl (meth)acrylate in the technical field ), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the art, it is commonly called “dicyclopentenyl (meth)acrylate”). , dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate,
(meth)acrylic acid esters such as phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[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-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2 .1] bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate;
Styrene compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene;
(Meth)acrylonitrile, vinyl chloride, vinylidene chloride, (meth)acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, (meth)acrylic acid esters, styrene compounds and dicarbonylimide compounds are preferable in terms of reactivity in copolymerization and heat resistance of the copolymer, and methyl (meth)acrylate and n-butyl (meth)acrylate. , tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are more preferred. These are used alone or in combination.

[5] Resin (A)
Resin (A) is the following resin [K1] or [K2].
Resin [K1]: a copolymer composed of a structural unit (Aa) and a structural unit (Ab);
Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab) and a structural unit (Ac).
Resin (A) is preferably resin [K2]. Further, among the resin [K2], it is preferable that the structural unit (Ac1) and the structural unit (Ac2) are included as the structural unit (Ac).
When the resin (A) contains the structural unit (Ac1), its ratio is preferably 1 to 50 mol %, more preferably 5 to 40 mol %, based on the total structural units constituting the resin (A).
When the resin (A) contains the structural unit (Ac2), its ratio is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, based on the total structural units constituting the resin (A).

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

When the ratio of the structural units constituting the resin [K1] is within the above range, the storage stability of the curable resin composition, the heat resistance and mechanical strength of the resulting film are excellent, and the solvent resistance is excellent. It is preferable in that a cured film can be formed.

In the resin [K2], the ratio of each structural unit to the total structural units constituting the resin [K2] is the structural unit (Aa): 5 to 80 mol%,
Structural unit (Ab); 5 to 80 mol%,
Structural unit (Ac); preferably 1 to 70 mol%,
Structural unit (Aa); 5 to 60 mol%,
Structural unit (Ab); 5 to 60 mol%,
Structural unit (Ac); 3 to 60 mol%,
is more preferable.
When the resin [K2] contains only the structural unit (Ac1) as the structural unit (Ac),
Structural unit (Aa); 5 to 80 mol%,
Structural unit (Ab); 5 to 80 mol%,
Structural unit (Ac1); preferably 5 to 40 mol%,
Structural unit (Aa); 5 to 50 mol%,
Structural unit (Ab); 5 to 50 mol%,
Structural unit (Ac1); more preferably 10 to 40 mol %.
When the resin [K2] contains only the structural unit (Ac2) as the structural unit (Ac),
Structural unit (Aa); 5 to 80 mol%,
Structural unit (Ab); 5 to 80 mol%,
Structural unit (Ac2); preferably 1 to 70 mol%,
Structural unit (Aa); 5 to 50 mol%,
Structural unit (Ab); 5 to 50 mol%,
Structural unit (Ac2); more preferably 3 to 60 mol %.
When both the structural unit (Ac1) and the structural unit (Ac2) are included as the structural unit (Ac) in the resin [K2],
Structural unit (Aa); 5 to 50 mol%,
Structural unit (Ab); 5 to 50 mol%,
Structural unit (Ac1); 1 to 50 mol%,
Structural unit (Ac2); preferably 1 to 60 mol%,
Structural unit (Aa); 5 to 30 mol%,
Structural unit (Ab); 5 to 30 mol%,
Structural unit (Ac1); 10 to 40 mol%,
Structural unit (Ac2); more preferably 3 to 55 mol %.

When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the curable resin composition, the heat resistance and mechanical strength of the resulting film are excellent, and the cured film is excellent in solvent resistance. is preferable in terms of obtaining Resin [K2] can be produced by the same method as resin [K1].

The polystyrene equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000, and particularly preferably is between 5,000 and 20,000. When 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 good, which is preferable.

The dispersity [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 degree of dispersion is within the above range, the obtained cured film tends to be more excellent in solvent resistance.
When the resin (A) contains the structural unit (Ac1), its acid value (in terms of solid content) 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, more 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 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 have excellent adhesion to the substrate.

The resin (A) is obtained by polymerizing a monomer leading to the structural unit (Aa), a monomer leading to the structural unit (Ab), and optionally a monomer leading to the structural unit (Ac). can be done.
Examples of the polymerization reaction include the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, March 1, 1972).

Specifically, a predetermined amount of a monomer leading to the structural unit (Aa), a monomer leading to the structural unit (Ab), and optionally a monomer leading to the structural unit (Ac), a polymerization initiator and A method of putting a solvent or the like into a reaction vessel and, for example, replacing oxygen with nitrogen to create a deoxygenated atmosphere and heating and keeping the temperature while stirring is exemplified.
In addition, a polymerization reaction of a monomer leading to the monomer (Aa') by the above polymerization method, a monomer leading to the structural unit (Ab), and a monomer leading to the structural unit (Ac) as necessary. Further, a method of forming the structural unit (Aa) by reacting the structural unit (Aa') with the compound (Aa'') can also be mentioned.
The polymerization initiator, solvent, and the like in the production of resin (A) are not particularly limited, and those commonly used in the relevant field can be used. Examples of polymerization initiators include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis(2,4-dimethylvaleronitrile), etc.) and 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 below-described solvents used in the curable resin composition.

The obtained resin may be used as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) obtained by a method such as reprecipitation. may 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 used as it is for the production of the curable resin composition, so that the curable resin composition The manufacturing process can be simplified.

The content of the resin (A) in the curable resin composition of the present invention is preferably 5 to 99% by mass, more preferably 10 to 98% by mass, based on the solid content in the curable resin composition. %.
When the content of the resin (A) is within the above range, the obtained cured film tends to be more excellent in solvent resistance. Here, the amount of solids in the curable resin composition refers to the amount obtained by removing the content of the solvent from the total amount of the curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.

<First additive (X)>
The first additive (X) is at least one compound selected from the group consisting of quaternary ammonium salts, quaternary phosphonium salts and tertiary sulfonium salts.

[1] Quaternary Ammonium Salt Examples of the quaternary ammonium salt include compounds represented by formula (IV).

[In formula (IV), R ⁴¹ to R ⁴⁴ each independently represent a hydrocarbon group having 1 to 24 carbon atoms which may have a substituent.
Y ^z- represents a z-valent anion.
z represents an integer of 1 to 3; ]

Examples of hydrocarbon groups having 1 to 24 carbon atoms in R ⁴¹ to R ⁴⁴ 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, aryl groups having 6 to 24 carbon atoms and aralkyl groups having 7 to 24 carbon atoms, etc., preferably alkyl groups having 1 to 24 carbon atoms and aryl groups having 6 to 24 carbon atoms. mentioned.

The number of carbon atoms in R ⁴¹ to R ⁴⁴ is preferably 4 to 100 as the total number of carbon atoms per molecule of the compound represented by formula (IV).
Examples of the substituent that the hydrocarbon group may have include a halogen atom, a cyano group, an acyl group, an acyloxy group, a carboxy group and an alkoxy group.
The cations of the compound represented by formula (IV) include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion, tri-n-octylmethylammonium ion, hexadecyl trimethylammonium ion, benzyltrimethylammonium ion, benzyltriethylammonium ion, hexadecylbenzyldimethylammonium ion, phenyltrimethylammonium ion and phenyltriethylammonium ion, preferably tetramethylammonium ion, tetraethylammonium ion, tetra-n- Examples include propylammonium ion, tetra-n-butylammonium ion and tri-n-octylmethylammonium ion.
Y ^z- in formula (IV) includes, for example, halide ions such as chloride ion, fluoride ion, bromide ion and iodide ion; sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion and hydroxide ion; carboxylate ion such as acetate ion, benzoate ion and salicylate ion; sulfonate ion such as benzenesulfonate ion, p-toluenesulfonate ion and trifluoromethanesulfonate ion; phenoxide ion and p-nitrophenoxide phenolate ions such as ions; tetrafluoroborate ions, hexafluorophosphate ions and tetraphenylborate ions, preferably halide ions, carboxylate ions, sulfonate ions and phenoxide ions.

The compound represented by formula (IV) is formed from any one selected from the above cations and any one selected from Y ^{2 z-} .
Examples of quaternary ammonium ions other than the compound represented by formula (IV) include hexadecylpyridinium ion, N-dodecylpyridinium ion, N-benzyl-2-methylpyridinium ion, N,N,N,N' , N′,N′-hexamethyl-1,5-pentanediaminium ion and N,N,N,N′,N′,N′-hexamethyl-1,5-hexanediaminium ion.
A quaternary ammonium salt may be an inner salt containing a carboxylate or sulfonate ion in the molecule.

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

[2] Quaternary Phosphonium Salt Examples of the quaternary phosphonium salt include compounds represented by the formula (V).

[In formula (V), R ⁵¹ to R ⁵⁴ each independently represent a hydrocarbon group having 1 to 24 carbon atoms.
Y ^y- represents a y-valent anion.
y represents an integer of 1 to 3; ]

Examples of hydrocarbon groups having 1 to 24 carbon atoms in R ⁵¹ to R ⁵⁴ 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, aryl groups having 6 to 24 carbon atoms and aralkyl groups having 7 to 24 carbon atoms, etc., preferably alkyl groups having 1 to 24 carbon atoms and aryl groups having 6 to 24 carbon atoms. mentioned.

The quaternary phosphonium ion in formula (V) includes tetraethylphosphonium ion, tetra-n-butylphosphonium ion, tri-n-octylethylphosphonium ion, hexadecyltriethylphosphonium ion, hexadecyltri-n-butylphosphonium ion, Examples include n-butyltriphenylphosphonium ion, n-pentyltriphenylphosphonium ion, methyltriphenylphosphonium ion, benzyltriphenylphosphonium ion and tetraphenylphosphonium ion.

Y ^y- in formula (V) includes the same anions as Y ^z- in formula (IV), preferably a halide ion.
Preferred quaternary phosphonium salts are tetraethylphosphonium bromide, tetra-n-butylphosphonium chloride and tetra-n-butylphosphonium acetate.

[3] Tertiary sulfonium salt Examples of the tertiary sulfonium salt include compounds represented by formula (VI).

[In formula (VI), R ⁶¹ to R ⁶³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms.
Y ^x- represents an x-valent anion.
x represents an integer of 1 to 3; ]

Examples of hydrocarbon groups for 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. groups, aryl groups having 6 to 24 carbon atoms and aralkyl groups having 7 to 24 carbon atoms, preferably alkyl groups having 1 to 24 carbon atoms and aryl groups having 6 to 24 carbon atoms.
Examples of the tertiary sulfonium ion in formula (VI) include di-n-butylmethylsulfonium ion, tri-n-butylsulfonium ion, dihexylmethylsulfonium ion, dicyclohexylmethylsulfonium ion and dodecylmethylethylsulfonium ion. be done.

Y ^x- in formula (VI) includes the same anions as Y ^z- in formula (IV), with halide ions being preferred.

Preferred tertiary sulfonium salts include, for example, di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate and dodecylmethylethylsulfonium chloride.

The content of the first additive (X) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1 to 7 parts by mass, relative to 100 parts by mass of the resin (A). part by mass. When the content of the first additive (X) is within the above range, the solvent resistance of the cured film formed from the curable resin composition containing it tends to be further improved, which is preferable.

<Second additive (Y)>
The second additive (Y) is at least one compound selected from the group consisting of epoxy compounds and 5-membered ring carbonate compounds.

[1] Epoxy compound An epoxy compound is a compound having one or more, preferably two or more oxiranyl 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 preferably a compound having 10 or less, more preferably 6 or less oxiranyl groups.

In the curable resin composition of the present invention, the following epoxy compounds are preferably used as the second additive (Y).

[2] Five-membered ring carbonate compound The five-membered ring carbonate compound has at least one five-membered ring carbonate structure, preferably two or more five-membered ring carbonate structures in the molecule.
Five-membered ring carbonate compounds include 1,3-dioxolan-2-one, 4-butyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, allylsuccinic acid anhydride, 4-(meth)acryloyloxymethyl-1,3-dioxolan-2-one, 4-allyloxymethyl-1,3-dioxolan-2-one and 4-vinyloxymethyl-1,3-dioxolan- 2-one and the like.

The content of the second additive (Y) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin (A). When the content of the second additive (Y) is within the above range, the solvent resistance of the cured film formed from the curable resin composition containing it tends to be further improved, which is preferable.

The weight ratio of the first additive (X) and the second additive (Y) is preferably 1:1 to 1:20 for the first additive (X):second additive (Y), More preferably 1:1 to 1:10, 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 an active radical or the like generated from the polymerization initiator (D) by light irradiation or the like, and examples thereof include compounds having an ethylenically unsaturated bond. and preferably (meth)acrylic compounds.
Examples of the compound having one ethylenically unsaturated bond include the same compounds as the monomers leading to the structural units constituting the resin (A).

Compounds having two ethylenically unsaturated bonds include 1,3-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 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, bisphenol A bis( acryloyloxyethyl) ether, 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.

Compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene oxide-modified trimethylol. Propane tri(meth)acrylate, propylene oxide-modified 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, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tri(meth)acrylate and acid anhydride reaction product, dipentaerythritol penta(meth)acrylate and acid anhydride reaction product, 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, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, reaction of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride and caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride reaction products and the like.
As the compound having an ethylenically unsaturated bond, a compound having three or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa(meth)acrylate is more preferable. These compounds may be used alone or in combination of two or more.

When the curable resin composition of the present invention contains a polymerizable compound (C), its content is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, relative to 100 parts by mass of the resin (A). Department. 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 it tend to be improved, which is preferable. .

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that generates an active radical, an acid, etc. by the action of light or heat and can initiate polymerization of the polymerizable compound (C). agent can be used.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds, A polymerization initiator containing an O-acyloxime compound is more preferred. When the polymerization initiator (D) is one of these polymerization initiators, the curable resin composition containing them has high sensitivity and the visible light region of the cured film formed from the curable resin composition containing the same. There is a tendency for the transmittance in

An O-acyloxime compound is a compound having a partial structure represented by formula (D1).
Below, * represents a bond.

Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 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-carbazole- 3-yl]-3-cyclopentylpropane-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1 -on-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01 and OXE02 (manufactured by BASF Corporation), N-1919, NCI-831 and NCI-930 (manufactured by ADEKA Corporation) may also be used.

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

Examples of compounds having a partial structure represented by formula (D2-1) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1 - on. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF Corporation) may also be used. Also, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-T-2002-544205, may be used. Examples of compounds having a partial structure represented by formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α- Included are diethoxyacetophenone and benzyl dimethyl ketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (D2-1).

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxy naphthyl)-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 and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. be done.

Acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may also be used.

Biimidazole compounds include, for example, 2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenylbiimidazole, 2,2′-bis(2,3-dichlorophenyl)-4 ,4′,5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis(2-chlorophenyl)-4, 4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403, JP-A-62-174204, etc.) and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

Furthermore, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3′,4,4′-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These can be used in combination with a polymerization initiation aid (H) (especially amines) described below.
When the curable resin composition of the present invention contains a polymerization initiator (D), the content thereof is preferably 0 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). .1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 5 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 it tends to have more excellent solvent resistance and high visible light transmittance. be.

<Polymerization initiation aid (H)>
The polymerization initiation aid (H) is used together with the polymerization initiator (D) and is a compound used to promote the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D), or an additive. It is a sensitizer.

Examples of polymerization initiation aids (H) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the thiazoline compound include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A-2008-65319, and the like.

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl 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.) may also be used.

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxy anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Carboxylic acid compounds 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 (H), its content is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation aid (H) is within the above range, the curable resin composition containing it tends to have higher sensitivity when forming a pattern.

<Leveling agent (B)>
Examples of the leveling agent (B) include silicone surfactants (containing no fluorine atoms), fluorine surfactants (containing no silicon atoms), and silicone surfactants having fluorine atoms. be done. These may have a polymerizable group in the side chain.

Examples of silicone-based surfactants (containing no fluorine atoms) include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name, manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, and 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 LLC), etc. .

Examples of the fluorosurfactant (which does not contain a silicon atom) include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, Florard FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Florado F171, Flora F172, Flora F173, Flora F177, Flora F183, Flora F554 R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemicals Laboratory Co., Ltd.).

Examples of the fluorine atom-containing silicone-based surfactants include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, F477 and F443 (manufactured by DIC Corporation) and the like can be mentioned.

As the leveling agent (B), a fluorosurfactant (which does not contain a silicon atom) is preferred.
When the leveling agent (B) is contained, its content is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.2% by mass or less, relative to the solid content in the curable resin composition. 002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.1% by 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 the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.
Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.
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, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and 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, phenetol and methylanisole and the like.
Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy ethyl propionate, 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, diethylene glycol monobutyl ether acetate and the like.
Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. etc.
Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.
Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.
Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

Among the above solvents, organic solvents having a boiling point of 100 to 200° C. at 1 atm are preferred from the viewpoint of coating properties and drying properties. Preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate, and propylene glycol monomethyl ether. More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate.

The content of the solvent (E) in the curable resin composition of the present invention is preferably 60-95% by mass, more preferably 70-95% 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 5-40% by mass, more preferably 5-30% by mass. When the content of the solvent (E) is within the above range, the coating properties of the curable resin composition tend to be good.
<Colorant (K)>
The curable resin composition of the present invention may contain a coloring agent (K). Colorants (K) include dyes and/or pigments. These coloring agents may be used alone or in combination of two or more. In that case, a combination of only dyes, a combination of only pigments, or a combination of dyes and pigments may be used.

Dyes are not particularly limited and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Staining Note (Shikisensha). be done. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin Dyes, quinoline dyes, nitro dyes, and the like.
Specifically, C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described.), 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 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. C.I. I. solvent dyes,
C. I. 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 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, 195, 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 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 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, 127, 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 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 and the like. I. acid dye,
C. I. 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 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 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. 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 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, 170, 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 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I. I. disperse dyes,
C. I. Basic Red 1, 10;
C. I. basic 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; I. basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C.I. Reactive Red 36; I. reactive dyes,
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 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, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant 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. Modant 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. C.I. I. modant dye,
C. I. C.I. I. and vat dyes.
Further, the dyes described in JP-A-2010-32999, JP-A-4492760, JP-A-2013-50693 and JP-A-2013-178478 are included.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

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

Examples of pigments include C.I. 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, yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58, 59;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

Among them, C.I. I. Pigment Yellow 138, 139, 150, C.I. I. Pigment Red 177, 242, 254, C.I. I. Pigment Red Violet 23, C.I. I. Pigment Blue 15:6 and C.I. I. It preferably contains at least one pigment selected from Pigment Green 7, 36, 58 and 59. These pigments may be used alone or in combination of two or more.

If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., and atomization by a sulfuric acid atomization method, etc. A treatment, a washing treatment with an organic solvent or water for removing impurities, a treatment for removing ionic impurities by an ion exchange method, or the like may be performed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These may be used alone or in combination of two or more. Specifically, the product names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (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), and the like.
When a pigment dispersant is used, the amount used is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of pigments.
When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.
When the curable resin composition of the present invention contains a coloring agent (K), its content is preferably 5 to 70% by mass, more preferably 8 to 65% by mass, more preferably 8 to 65% by mass, based on the total amount of solid content. is 10 to 60% by mass. When the content of the coloring agent (K) is within the above range, the desired chromaticity can be obtained.

<Other ingredients>
The curable resin composition of the present invention may optionally contain additives known in the art such as fillers, other polymer compounds, antioxidants, ultraviolet absorbers, chain transfer agents, adhesion promoters, etc. may contain.

When the curable resin composition of the present invention does not contain a coloring agent, 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 to 700 nm. , its average transmittance is preferably 70% or more, more preferably 80% or more.

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

[Method for producing curable resin composition]
The curable resin composition of the present invention comprises a resin (A), a first additive (X) and a second additive (Y), and optionally used a solvent (E) and a polymerizable compound (C). , a polymerization initiator (D), a polymerization initiation aid (H), a leveling agent (B), a colorant (K) and other components can be mixed by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 5 μm.

[Method for producing cured film]
The cured film of the present invention can be produced by applying the curable resin composition of the present invention onto a substrate, drying and then heating. More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).
Step (1): a step of applying the curable resin composition of the present invention to a substrate;
Step (2): A step of drying the curable resin composition after application under reduced pressure and/or heating to form a composition layer;
Step (3): A step of heating the composition layer.

Moreover, when the curable resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), a cured film having a pattern can be produced by performing the following steps.
Step (1): a step of applying the curable resin composition of the present invention to a substrate;
Step (2): A step of drying the curable resin composition after application under reduced pressure and/or heating to form a composition layer;
Step (2a): a step of exposing the composition layer through a photomask;
Step (2b): a step of developing the composition layer after exposure;
Step (3a): A 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 (underlying substrate).
Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, a driving circuit, and the like may be formed on the substrate. Coating onto the substrate is preferably carried out using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Step (2) is a step of drying the applied curable resin composition under reduced pressure and/or by heating to form a composition layer. By performing this step, volatile components such as solvents in the curable resin composition are removed. Vacuum drying is preferably carried out at a temperature range of 20 to 25°C under a pressure of 50 to 150Pa. Heat drying (pre-baking) may be performed before or after vacuum drying.
Heat drying is usually performed using a heating device such as an oven or a hot plate. The temperature for drying by heating is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

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

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. The photomask used has a light-shielding portion corresponding to a 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. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You can Light sources include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an exposure apparatus such as a mask aligner, a stepper, etc., because it is possible to uniformly irradiate the entire exposure surface with parallel rays and to perform accurate alignment between the photomask and the composition layer.

Step (2b) is a step of developing the composition layer after exposure. By contacting the exposed composition layer with a developer for development, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a patterned composition layer on the substrate. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01-10 mass %, more preferably 0.03-5 mass %. Furthermore, the developer may contain a surfactant. The developing method may be any of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate may be tilted at any angle during development. It is preferable to wash with water after development.

Step (3a) is a step of heating the composition layer after development. By heating in the same manner as in step (3), the patterned composition layer is cured to form a patterned cured film on the substrate.

According to the curable resin composition of the present invention, a cured film having excellent solvent resistance can be produced even when cured at a low temperature such as 140°C to 150°C. The cured film is useful as a photospacer, overcoat, and interlayer insulating film used in display devices. Moreover, when the curable resin composition of the present invention contains a colorant, it is useful as a color filter used in display devices such as liquid crystal display devices, organic EL devices, and electronic paper, and solid-state imaging devices.

The present invention will be described in more detail below by way of examples. Unless otherwise specified, "%" and "parts" in the examples mean % by mass and parts by mass.

(Synthesis Example 1: Synthesis of copolymer (a1))
A flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel was charged with 80 parts of propylene glycol monomethyl ether and heated to 90°C. 41.3 parts of vinyl toluene, 26.6 parts of 2-(1,3-dioxobutyloxy)ethyl methacrylate, 27.1 parts of methacrylic acid, 5 parts of azobis(isobutyronitrile), and 30 parts of propylene glycol monomethyl ether. Continuous dropping of the mixed solution into the flask was started using a dropping funnel. The temperature inside the flask was kept at 90±1° C. during the dropwise addition of the mixed solution, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was raised to 90±1° C. and maintained for 6 hours. After the reaction, the reaction solution is cooled to 40° C. or less, 0.12 parts of 4-methoxyphenol, 22.6 parts of 3,4-epoxycyclohexylmethyl acrylate, 4.7 parts of triphenylphosphine, and 90 parts of propylene glycol monomethyl ether. After raising the temperature in the flask to 110 ° C., an addition reaction is performed at a temperature in the flask of 110 ± 1 ° C. to obtain a copolymer (a1) solution having a solid content of 36.5%. Obtained. The copolymer (a1) had a weight average molecular weight (Mw) of 16,500, a dispersity of 2.4, and an acid value of 92 mg-KOH/g in terms of solid content. The copolymer (a1) has the following structural units.

(Synthesis Example 2: Synthesis of copolymer (a2))
A flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel was charged with 70 parts of propylene glycol monomethyl ether and heated to 90°C. 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), propylene glycol monomethyl ether A solution in which 30 parts were mixed was continuously dropped into the flask using a dropping funnel. The temperature inside the flask was kept at 90±1° C. during the dropwise addition of the mixed solution, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was raised to 90±1° C. and maintained for 6 hours. After the reaction, the reaction solution is cooled to 40° C. or less, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate, 4.7 parts of triphenylphosphine, and 85 parts of propylene glycol monomethyl ether. After raising the temperature in the flask to 110 ° C., an addition reaction is performed at a temperature in the flask of 110 ± 1 ° C. to obtain a copolymer (a2) solution with a solid content of 37.9%. Obtained. The obtained copolymer (a2) had a weight average molecular weight (Mw) of 14,300, a dispersity of 2.4, and an acid value converted to solid content of 103 mg-KOH/g. The copolymer (a2) has the following structural units.

(Synthesis Example 3: Synthesis of copolymer (a3))
A flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel was charged with 70 parts of propylene glycol monomethyl ether and heated to 90°C. 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), 30 parts of propylene glycol monomethyl ether Continuous dropping of the mixed solution into the flask was started using a dropping funnel.
The temperature inside the flask was kept at 90±1° C. during the dropwise addition of the mixed solution, and the dropwise addition was completed in 3 hours. After completion of dropping, the temperature inside the flask was raised to 90±1° C. and maintained for 6 hours. After the reaction, the reaction solution is cooled to 40° C. or less, and 0.12 parts of 4-methoxyphenol, 24.4 parts of 3,4-epoxycyclohexylmethyl acrylate, 5 parts of triphenylphosphine, and 95 parts of propylene glycol monomethyl ether are added. After the temperature in the flask was raised to 110° C., an addition reaction was performed at the temperature in the flask of 110±1° C. to obtain a copolymer (a3) solution with a solid content of 38.5%. . The obtained copolymer (a3) had a weight average molecular weight (Mw) of 15,800, a dispersity of 2.4, and an acid value converted to solid content of 80 mg-KOH/g. The copolymer (a3) has the following structural units.

(Synthesis Example 4: Synthesis of resin (a))
100 parts of propylene glycol monomethyl acetate was introduced into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while being replaced with nitrogen and heated to 120°C. Next, a mixture of 43 parts of methyl methacrylate, 25 parts of methacrylic acid and 0.68 parts of tert-butylperoxy-2-ethylhexanoate (perbutyl O; manufactured by NOF Corporation) was added from a dropping funnel for 2 hours. The mixture was added dropwise to the flask and stirred at 120° C. for 2 hours to obtain a copolymer. Next, the inside of the flask is replaced with air, 10 parts of glycidyl methacrylate, 0.44 parts of triphenylphosphine and 0.08 parts of methylhydroquinone are added to the above copolymer solution, and the reaction is continued at 120° C. to obtain a solid content acid value. was 100 mg-KOH/g, the reaction was terminated. By adding 50 parts of propylene glycol monomethyl acetate, a resin (a) solution having a solid content of 40% was obtained. Resin (a) had a weight average molecular weight (Mw) of 30,000, a dispersity of 2.5, and an acid value of 100 mg-KOH/g in terms of solid content. 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.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL/min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw/Mn) of the polystyrene equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) obtained above was taken as the degree of dispersion.
(Synthesis Example 5: Synthesis of Compound Represented by Formula (A-IV))
20 parts of the compound represented by formula (1x) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was heated at 110°C. Stirred for 6 hours. After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour to precipitate crystals. Precipitated crystals were obtained as a residue of suction filtration and dried to obtain a compound represented by formula (A-IV).

Identification of compounds of formula (A-IV) (mass spectrometry) ionization mode = ESI+: m/z = [M+H] ⁺ 659.3
Exact Mass: 658.3

[Examples 1 to 19, 21 to 23, Comparative Examples 1 and 2]
<Preparation of curable resin composition>
Each component shown in Table 1 is contained in the ratio 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 (mixing ratio is 1:1 in mass ratio) 1), and mixed so as to have a solid content concentration shown in Table 1 to obtain a curable resin composition. In Table 1, the number of parts of each component represents parts by mass in terms of solid content.

Copolymer (a1): Copolymer obtained in Synthesis Example 1 Copolymer (a2): Copolymer obtained in Synthesis Example 2 Copolymer (a3): Copolymer obtained in Synthesis Example 3 Coalesced resin (a): copolymer obtained in Synthesis Example 4 (x1): tetrabutylammonium chloride (x2): tetrabutylammonium p-nitrophenoxide (x3): tetrabutylammonium bromide (x4): tetrasalicylate Butyl ammonium (x5): tetrabutylammonium nitrate (x6): tetrabutylammonium trifluoromethanesulfonate (x7): tetrabutylammonium hydrogen sulfate (x8): 3-[dimethyl(tetradecyl)ammonio]propane-1-sulfonate (above , manufactured by Tokyo Chemical Industry Co., Ltd.)
(y1): a compound represented by the following formula (ED-529; manufactured by ADEKA Corporation)

(y2): a compound represented by the following formula (DA-MGIC; manufactured by Shikoku Kasei Co., Ltd.)

(y3): a compound represented by the following formula (MA-DGIC; manufactured by Shikoku Kasei Kogyo Co., Ltd.)

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

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

(y6): a compound represented by the following formula (TG-G; manufactured by Shikoku Kasei Kogyo Co., Ltd.)

(y7): a compound represented by the following formula (S-500; manufactured by SYNASIA)

(y8): a compound represented by the following formula (S-186; manufactured by SYNASIA)

(y9): a compound represented by the following formula (S-400; manufactured by SYNASIA)

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

<Preparation of cured film 1>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was washed with a neutral detergent, water and isopropanol in that order, and then dried. A curable resin composition was spin-coated on this substrate so that the film thickness after post-baking was 1.5 μm. Next, it was dried under reduced pressure with a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) at a rotary pump speed of 1000 rpm, a booster pump speed of 700 rpm, and a normal temperature of 25° C. until the degree of pressure reduction reached 66 Pa. After that, it was baked on a hot plate at 140° C. for 3 minutes to obtain a cured film.

<Solvent resistance evaluation>
The resulting 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 before immersion and after water washing (film thickness before immersion is t1, film thickness after water washing is t2) is measured, and the ratio of the film thickness after water washing to the film thickness before immersion (t2/t1 ) was calculated. A film thickness measurement device (DEKTAK XT; manufactured by Japan Vacuum Engineering Co., Ltd.) was used for film thickness measurement. Table 1 shows the results.

[Example 20]
<Preparation of curable resin composition>
C. I. Pigment Blue 15:6 23.5 parts, 8.2 parts of acrylic pigment dispersant, and 193 parts of propylene glycol monomethyl ether acetate are mixed, the pigment is sufficiently dispersed using a bead mill, and then
Compound represented by formula (A-IV) (dye) 6.2 parts Copolymer (a1) 60 parts (solid content conversion)
Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts Polymerization initiator (NCI-930; manufactured by ADEKA Corporation; O-acyl oxime compound)
16 parts above (x1) 2 parts above (y6) 6 parts diacetone alcohol 20 parts propylene glycol monomethyl ether acetate 783 parts and leveling agent 0.1 part were mixed to obtain a curable resin composition.
<Preparation of cured film 2>
A curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; Corning Incorporated) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a composition layer. After standing to cool, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) was used in an air atmosphere at 80 mJ/cm ² . (365 nm standard). A photomask having a 1:1 line-and-space pattern of 100 μm was used as the photomask. The composition layer after light irradiation is developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23° C. for 60 seconds, washed with water, and placed on a hot plate. and baked at 150° C. for 5 minutes to obtain a cured film having a pattern.
From the curable resin composition of Example 20, the cured film prepared by the method of preparation 2 of the cured film was evaluated for solvent resistance in the same manner as described above. As a result, (t2/t1) was 1. .

ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which can form the cured film excellent in solvent resistance can be provided, and this cured film is suitable for a display apparatus etc.

Claims (3)

including a resin (A), a first additive and a second additive,
The resin (A) is a copolymer containing a structural unit (Aa) having an α,β-unsaturated carbonyl group, a structural unit (Ab) having an active methylene group or an active methine group, and a structural unit (Ac1) having an acid group. is a coalescence,
The structural unit (Ac1) having an acid group is (meth)acrylic acid,
The first additive is a quaternary ammonium salt,
The curable resin composition, wherein the second additive is an epoxy compound. 2. The curable resin composition according to claim 1, wherein said epoxy compound is an epoxy compound having at least two oxiranyl groups in one molecule. A cured film formed from the curable resin composition according to claim 1 or 2.