JP6175754B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  In recent liquid crystal display devices, a curable resin composition is used to form a cured film such as a photo spacer or an overcoat. As such a curable resin composition, a composition containing diethylene glycol ethyl methyl ether, 3-methoxy-1-butanol, and propylene glycol monomethyl ether as solvents is known (Patent Document 1).

JP 2010-152335 A

  In the conventionally proposed curable resin compositions, the drying time for drying under reduced pressure after applying the curable resin composition to a substrate is long and may not always be satisfactory.

The present invention includes the following inventions.
[1] including a curable resin and a solvent;
The solvent includes dialkylene glycol dialkyl ether, solvent (E1), and solvent (E2),
A curable resin composition, wherein the content of dialkylene glycol dialkyl ether is 1% by mass or more and 45% by mass or less based on the total amount of the solvent.
Solvent (E1): Different from dialkylene glycol dialkyl ether, and the evaporation rate is 40 or more and 100 or less when the evaporation rate of butyl acetate is 100. Solvent (E2): What is dialkylene glycol dialkyl ether? The solvent [2] which is different and has an evaporation rate of 13 or more and less than 40 when the evaporation rate of butyl acetate is 100, and the resin having curability comprises an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride [1] A copolymer comprising a structural unit derived from at least one selected from the group consisting of a structural unit derived from a monomer having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond. Curable resin composition.
[3] The curable resin composition according to [1] or [2], further comprising an antioxidant.
[4] A cured film formed from the curable resin composition according to any one of [1] to [3].
[5] A display device comprising the cured film according to [4].
[6] (1) A step of applying the curable resin composition according to any one of [1] to [3] to a substrate, and (2) a composition layer by drying the curable resin composition after application under reduced pressure. And (3) a step of heating the composition layer.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition with short drying time at the time of drying under reduced pressure after apply | coating a curable resin composition to a board | substrate.

  In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

The curable resin composition of the present invention includes a curable resin (hereinafter sometimes referred to as “resin (A)”) and a solvent (E).
The solvent (E) includes dialkylene glycol dialkyl ether, the solvent (E1), and the solvent (E2),
It is a curable resin composition whose content of dialkylene glycol dialkyl ether is 1% by mass or more and 45% by mass or less with respect to the total amount of the solvent.
Solvent (E1): Different from dialkylene glycol dialkyl ether, and the evaporation rate is 40 or more and 100 or less when the evaporation rate of butyl acetate is 100. Solvent (E2): What is dialkylene glycol dialkyl ether? Different and the evaporation rate is 13 or more and less than 40 when the evaporation rate of butyl acetate is 100

  Furthermore, the curable resin composition of the present invention includes a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter sometimes referred to as “(meth) acryloyl group”) (hereinafter referred to as “ It may preferably be referred to as “(meth) acrylic compound (B)”), an antioxidant (F), and at least one component selected from the group consisting of a surfactant (H).

  The curable resin composition of the present invention is at least one epoxy resin selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter sometimes referred to as “epoxy resin (C)”). , A polymerization initiator (D), a polymerization initiation assistant (D1), a thiol compound (T), a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. And may contain at least one component selected from the group consisting of imidazole compound (J).

<Resin (A)>
Resin (A) is a curable resin, preferably a thermosetting resin, more preferably a resin curable by heat of 60 ° C. or higher, and selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. A monomer having a structural unit derived from at least one kind (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond (hereinafter “(b)”) A copolymer containing a structural unit derived from The copolymer is further derived from a monomer that is copolymerizable with (a) and does not have a cyclic ether structure having 2 to 4 carbon atoms (hereinafter sometimes referred to as “(c)”). You may have a structural unit.
The resin (A) is preferably the following resin [K1] and resin [K2].
Resin [K1]: Copolymer of (a) and (b);
Resin [K2]: a copolymer of (a), (b) and (c).

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, (meth) acrylic acid and maleic anhydride are preferable, and (meth) acrylic acid is more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

  (B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”). It is done.

  (B1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

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

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^b1 and R ^b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O—, * —CH ₂ CH ₂ —O—, and more preferably a single bond, * —CH _2. CH ₂ —O— can be mentioned. * Represents a bond with O.

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

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

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or as a mixture in any ratio. When used as a mixture, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

(B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
(B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  (B3) is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the cured film to be obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, 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] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoints of copolymerization reactivity and heat resistance. .

In the resin [K1], the ratio of the structural units derived from the respective monomers is relative to the total structural units constituting the resin [K1].
Structural unit derived from (a); 5 to 60 mol%
Structural unit derived from (b); 40-95 mol%
Is preferred,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
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 chemical resistance of the resulting cured film, the heat resistance, and the mechanical strength tend to be excellent. .

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent capable of dissolving each monomer may be used, and examples thereof include a solvent described later used for the curable resin composition.

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

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2 to 40 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5-35 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 1-60 mol%
It is more preferable that
Further, the total amount of the structural unit derived from (a) and the structural unit derived from (b) is preferably 70 to 99 mol% with respect to the total number of moles of all structural units constituting the resin [K2]. 90 to 99 mol% is more preferable.
When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the curable resin composition, the chemical resistance, the heat resistance, and the mechanical strength of the resulting cured film tend to be excellent.
Resin [K2] can be manufactured by the same method as resin [K1].

  Specific examples of the resin [K1] include (meth) acrylic acid / a compound represented by formula (I-1) (hereinafter sometimes abbreviated as “formula (I-1)”. Formula (I-2) Etc., etc.), (meth) acrylic acid / copolymer of formula (I-2), (meth) acrylic acid / copolymer of formula (I-3), (meta ) Acrylic acid / copolymer of formula (I-4), (meth) acrylic acid / copolymer of formula (I-5), (meth) acrylic acid / copolymer of formula (I-6), (Meth) acrylic acid / copolymer of formula (I-7), (meth) acrylic acid / copolymer of formula (I-8), (meth) acrylic acid / copolymer of formula (I-9), (Meth) acrylic acid / copolymer of formula (I-10), (meth) acrylic acid / copolymer of formula (I-11), (meth) acrylic acid / copolymer of formula (I-12) , (Meta) Copolymer of crylic acid / formula (I-13), copolymer of (meth) acrylic acid / formula (I-14), copolymer of (meth) acrylic acid / formula (I-15), (meth ) Acrylic acid / copolymer of formula (II-1), (meth) acrylic acid / copolymer of formula (II-2), (meth) acrylic acid / copolymer of formula (II-3), (Meth) acrylic acid / copolymer of formula (II-4), (meth) acrylic acid / copolymer of formula (II-5), (meth) acrylic acid / copolymer of formula (II-6), (Meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / copolymer of formula (II-8), (meth) acrylic acid / copolymer of formula (II-9) , (Meth) acrylic acid / copolymer of formula (II-10), (meth) acrylic acid / copolymer of formula (II-11), (meth) acrylic acid / formula (I -12), (meth) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / copolymer of formula (II-14), (meth) acrylic acid / formula ( Copolymer of (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1), (meth) acrylic acid / formula (I-2) / formula (II- 2) copolymer, (meth) acrylic acid / copolymer of formula (I-3) / formula (II-3), (meth) acrylic acid / formula (I-4) / formula (II-4) Copolymer, (meth) acrylic acid / copolymer of formula (I-5) / formula (II-5), copolymer of (meth) acrylic acid / formula (I-6) / formula (II-6) Polymer, copolymer of (meth) acrylic acid / formula (I-7) / formula (II-7), copolymer of (meth) acrylic acid / formula (I-8) / formula (II-8) , (Meth) acrylic acid / formula (I-9) / copolymer of formula (II-9), (meth) acrylic acid / copolymer of formula (I-10) / copolymer of formula (II-10), (meth) acrylic acid / formula (I -11) / copolymer of formula (II-11), (meth) acrylic acid / copolymer of formula (I-12) / copolymer of formula (II-12), (meth) acrylic acid / formula (I-13) ) / Copolymer of formula (II-13), (meth) acrylic acid / copolymer of formula (I-14) / copolymer of formula (II-14), (meth) acrylic acid / formula (I-15) / Copolymer of formula (II-15), copolymer of (meth) acrylic acid / formula (I-1) / formula (I-7), (meth) acrylic acid / formula (I-1) / formula ( II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / copolymer of formula (I-3) Crotonic acid / formula (I 4) copolymer, crotonic acid / copolymer of formula (I-5), crotonic acid / copolymer of formula (I-6), crotonic acid / copolymer of formula (I-7), croton Acid / copolymer of formula (I-8), crotonic acid / copolymer of formula (I-9), crotonic acid / copolymer of formula (I-10), crotonic acid / copolymer of formula (I-11) Copolymer, crotonic acid / copolymer of formula (I-12), crotonic acid / copolymer of formula (I-13), crotonic acid / copolymer of formula (I-14), crotonic acid / Copolymer of formula (I-15), copolymer of crotonic acid / formula (II-1), copolymer of crotonic acid / formula (II-2), copolymer of crotonic acid / formula (II-3) Polymer, crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / (II-7) copolymer, crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / copolymer of formula (II-10) Crotonic acid / copolymer of formula (II-11), crotonic acid / copolymer of formula (II-12), crotonic acid / copolymer of formula (II-13), crotonic acid / formula (II -14), crotonic acid / copolymer of formula (II-15), maleic acid / copolymer of formula (I-1), maleic acid / copolymer of formula (I-2), Maleic acid / copolymer of formula (I-3), maleic acid / copolymer of formula (I-4), maleic acid / copolymer of formula (I-5), maleic acid / copolymer of formula (I-6) ), Maleic acid / copolymer of formula (I-7), maleic acid / copolymer of formula (I-8), maleic acid / copolymer of formula (I-9), Rain acid / copolymer of formula (I-10), maleic acid / copolymer of formula (I-11), maleic acid / copolymer of formula (I-12), maleic acid / formula (I-13) ), Maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15), maleic acid / copolymer of formula (II-1), maleic acid / Copolymer of formula (II-2), maleic acid / copolymer of formula (II-3), maleic acid / copolymer of formula (II-4), maleic acid / copolymer of formula (II-5) Copolymer, maleic acid / copolymer of formula (II-6), maleic acid / copolymer of formula (II-7), maleic acid / copolymer of formula (II-8), maleic acid / formula (II-9) copolymer, maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11), maleic acid / formula (I -12), maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / copolymer of formula (II-15), (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-1), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-2), (meth) acrylic acid / Maleic anhydride / copolymer of formula (I-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-4), (meth) acrylic acid / maleic anhydride / formula (I-5) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-6), (meth) acrylic acid / maleic anhydride / formula (I-7) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-8), (meth) acrylic acid / maleic Anhydride / copolymer of formula (I-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-10), (meth) acrylic acid / maleic anhydride / formula (I -11), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-13) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-14), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) acrylic Acid / maleic anhydride / copolymer of formula (II-1), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-2), (meth) acrylic acid / maleic anhydride / Copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-4) Copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-5), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-6), (meth) acrylic Acid / maleic anhydride / copolymer of formula (II-7), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-8), (meth) acrylic acid / maleic anhydride / Copolymer of formula (II-9), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-10), (meth) acrylic acid / maleic anhydride / formula (II-11) ), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-13), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-14), (meth) a Copolymers of acrylic acid / maleic anhydride / formula (II-15) can be mentioned.

  Specific examples of the resin [K2] include a copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-2) / methyl (meth). Copolymer of acrylate copolymer, (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate (Meth) acrylic acid / formula (I-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate copolymer, ) Acrylic acid / Formula (I-7) / Methyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-8) / Methyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-9) / Methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (I-12) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (I-13) / methyl (meth) acrylate, (meth) acrylic Acid / formula (I-14) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula ( II-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-3) / Methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, (Meth) acrylic acid / formula (II-6) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate copolymer, (meth) acrylic Acid / formula (II-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-9) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula ( II-10) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-12) / Methyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate copolymer Polymer, Copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclo Pentanyl (meth) acrylate copolymer, crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate copolymer, maleic acid / formula (I-1) / dicyclopentanyl (meta ) Acrylate copolymer, Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / di Copolymer of cyclopentanyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, maleic acid / formula (II-1) / dicyclopentanyl ( (Meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) ) / Methyl (meth) acrylate / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate copolymer, ) Acrylic acid / Formula (II-1) / Phenyl (meth) acrylate copolymer, (Meth) acrylic acid / Formula (I-1) / Formula (II-1) / Phenyl (meth) acrylate copolymer , Crotonic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, maleic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride Product / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, crotonic acid / Copolymer of formula (II-1) / phenyl (meth) acrylate, maleic acid / copolymer of formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / Copolymer of formula (I-1) / diethyl maleate, (meth) acrylic acid / copolymer of formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate copolymer, crotonic acid / copolymer of formula (I-1) / diethyl maleate, maleic acid / copolymer of formula (I-1) / diethyl maleate, Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate Polymer, crotonic acid / formula ( I-1) / diethyl maleate copolymer, maleic acid / formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / maleic Copolymer of diethyl acid, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / diethyl maleate copolymer, (meth) acrylic acid / formula (I-1) / 2-hydroxy Copolymer of ethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, maleic acid / formula (I-1 ) / 2-Hide Copolymer of xylethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (I -1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula ( I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, Copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula (I-1 ) / Bicyclo [2.2.1] hept-2-ene copolymer, maleic acid / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meta ) Acrylic acid / maleic anhydride / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meta ) Acrylate / bicyclo [2.2.1] hept-2-ene copolymer, crotonic acid / formula (II-1) / bicyclo [2.2.1] hept 2-ene copolymer, maleic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / maleic anhydride / formula ( II-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / bicyclo [2.2.1] Copolymer of hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, corotate of crotonic acid / formula (I-1) / N-cyclohexylmaleimide Compound, maleic acid / formula (I-1) / N-cyclohex Rumaleimide copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (I-1) / methyl (meth) Copolymer of acrylate / N-cyclohexylmaleimide, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide Copolymer, (meth) acrylic acid / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (II-1) / styrene copolymer, A) Acrylic acid / Formula (I-1) / Formula (II-1) / Styrene copolymer, Crotonic acid / Formula (I-1) / Styrene copolymer, Maleic acid / Formula (I-1) / Styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Styrene copolymer, Crotonic acid / Formula (II-1) / Styrene copolymer, Maleic acid / Formula (II-1) / Styrene copolymer, (Meth) acrylic acid / Maleic anhydride / Formula (II-1) / styrene copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic / Copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, Crotonic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, maleic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene A copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / formula (II-1) / N-cyclohexylmale / Styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / formula (II-1) / Examples thereof include a methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer.

The weight average molecular weight in terms of polystyrene of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 20,000. Particularly preferred is 5,000 to 10,000. When the weight average molecular weight of the resin (A) is within the above range, the applicability of the curable resin composition tends to be good.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the obtained cured film tends to be excellent in chemical resistance.

  The acid value of the resin (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, particularly preferably 50 mg-KOH / g. It is 135 mg-KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the 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.

  Content of resin (A) becomes like this. Preferably it is 30-90 mass% with respect to solid content of the curable resin composition of this invention, More preferably, it is 35-80 mass%, More preferably, it is 40-70 mass. %. When the content of the resin (A) is within the above range, the resulting cured film tends to be excellent in heat resistance and excellent in adhesion to the substrate and chemical resistance. Here, solid content of curable resin composition means the quantity remove | excluding content of the solvent (E) from the total amount of the curable resin composition of this invention.

<(Meth) acrylic compound (B)>
The (meth) acrylic compound (B) is a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

  Examples of the (meth) acrylic compound (B) having one (meth) acryloyl group include the same compounds as those mentioned as the above (a), (b) and (c), and among them, (meth) acrylic acid Esters are preferred.

  Examples of the (meth) acrylic compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol (Meth) acrylate, 3-methyl-pentanediol di (meth) acrylate.

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripenta Erythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripen Erythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, Reaction product of pentaerythritol hepta (meth) acrylate and acid anhydride, 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, caprola Tone-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, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction of reaction product, caprolactone-modified tripentaerythritol hepta (meth) acrylate with acid anhydride Thing etc. are mentioned.
The (meth) acrylic compound (B) is preferably a (meth) acrylic compound having 3 or more (meth) acryloyl groups, and more preferably dipentaerythritol hexa (meth) acrylate.

  When the curable resin composition of the present invention contains a (meth) acrylic compound (B), the content thereof is preferably 20 to 100 parts by mass, more preferably 100 parts by mass of the resin (A). Is 25 to 70 parts by mass. When the content of the (meth) acrylic compound (B) is within the above range, the resulting cured film tends to have good chemical resistance and mechanical strength.

<Epoxy resin (C)>
The epoxy resin (C) is not particularly limited except that it has a different structure from the resin (A), but at least one selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins is preferable.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized by reacting phenols, polyhydric alcohols and the like with epichlorohydrin.
Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, and trishydroxyphenylmethane type epoxy resin. It is done.

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

  The epoxy resin (C) used in the curable resin composition of the present invention is glycidyl such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, polyphenol type epoxy resin, etc. An ether type epoxy resin is preferred. Among them, bisphenol A type epoxy resin is particularly preferable.

  The glycidyl ether type epoxy resin as described above can be synthesized by condensing a corresponding phenol and epichlorohydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by methods conventionally known to those skilled in the art. Moreover, you may use a commercial item. Examples of commercially available bisphenol A type epoxy resins include JER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), and the like. Examples of commercially available bisphenol F-type epoxy resins include Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Tohto Kasei Co., Ltd.), and the like. Commercially available phenol novolac epoxy resins include Epicoat 152, Epicoat 154 (Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (Nippon Kayaku Co., Ltd.), and DEN-438 (Dow Chemical Co., Ltd.). ) And the like. Examples of commercially available o-cresol novolac epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.). As a commercial item of a polyphenol type epoxy resin, Epicoat 1032H60, Epicoat YX-4000 (made by Mitsubishi Chemical Corporation), etc. are mentioned.

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

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

  When the curable resin composition of the present invention includes an epoxy resin (C), the content thereof is preferably 100 parts by mass of the total content of the resin (A) and the (meth) acrylic compound (B). 1-60 mass parts, More preferably, it is 5-50 mass parts. When the content of the epoxy resin (C) is within the above range, the resulting cured film tends to have excellent adhesion to the substrate.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound. More preferred is a polymerization initiator containing a sulfur compound. These polymerization initiators tend to be highly sensitive and have high transmittance in the visible light region.

Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミンが挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound 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] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Is mentioned. Commercial products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used. Moreover, you may use the polymerization initiator which has the group which can raise | generate chain transfer described in the Japanese translations of PCT publication No. 2002-544205 gazette.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyldimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  Examples of the triazine compound 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) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 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′-tetraphenylbiimidazole, 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 (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 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, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

An acid generator can also be used as the polymerization initiator (D).
Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples include benzoin tosylate.

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

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is used together with the polymerization initiator (D), and accelerates the polymerization of a polymerizable compound (for example, (meth) acrylic compound (B)) whose polymerization is initiated by the polymerization initiator (D). It is a compound or a sensitizer used for the preparation.

  Examples of the polymerization initiation assistant (D1) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

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

  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-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic 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 assistant (D1), the content is 100 parts by mass with respect to the total content of the resin (A) and the (meth) acrylic compound (B). Preferably it is 0.1-30 mass parts, More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (D1) is within the above range, it tends to be more sensitive when forming a pattern.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanyl group (—SH) in the molecule. Among them, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to a carbon atom of an aliphatic hydrocarbon structure is more preferable. The thiol compound (T) is preferably used together with the polymerization initiator (D).

  Examples of the thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), ethylene Glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris ( 3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl Squirrel (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane.

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

<Antioxidant (F)>
Examples of the antioxidant (F) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among these, a phenolic antioxidant is preferable in that the cured film is less colored.

Examples of phenolic antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methyl) Ruphenol), 2,2′-thiobis (6-tert-butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3 , 5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "- (Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert- Butyl-4-methylphenol and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [ 1, , 2] dioxaphosphepin and the like.
A commercial item may be used as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all are manufactured by BASF).

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3 -Lauryl thiopropionate). A commercially available product may be used as the sulfur-based antioxidant. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1, 3-Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite is mentioned. A commercially available product may be used as the phosphorus-based antioxidant. Examples of commercially available phosphorus antioxidants include Irgaphos (registered trademark) 168, 12, and 38 (all manufactured by BASF), Adeka Stub 329K, and Adeka Stub PEP36 (all manufactured by ADEKA).

  Examples of amine-based antioxidants include N, N′-di-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, and N, N′-dicyclohexyl-p-phenylene. Examples include diamine, N, N′-diphenyl-p-phenylenediamine, and N, N′-bis (2-naphthyl) -p-phenylenediamine. A commercially available product may be used as the amine-based antioxidant. Examples of commercially available amine-based antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

  When the curable resin composition of this invention contains antioxidant (F), the content is 0 with respect to 100 mass parts of total content of resin (A) and (meth) acrylic compound (B). It is preferably 1 part by mass or more and 5 parts by mass or less, and more preferably 0.5 part by mass or more and 3 parts by mass or less. When content of antioxidant (F) exists in the said range, the cured film obtained tends to be excellent in heat resistance and pencil hardness.

<Surfactant (H)>
Examples of the surfactant (H) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.

Examples of the silicone surfactant include surfactants having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F552, F553, F554, F555, F556, F556, F558, F559, R559 (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Materials Electronics Chemicals, Inc.) ), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  When the curable resin composition of this invention contains surfactant (H), the content is 0.001 mass% or more and 0.2 mass% or less with respect to the total amount of the curable resin composition of this invention. Preferably, it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (H) is within the above range, the flatness of the cured film can be improved.

<Polyvalent carboxylic acid (G)>
The polyvalent carboxylic acid (G) is at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of a polyvalent carboxylic acid. The polyvalent carboxylic acid (G) preferably has a molecular weight of 3000 or less, and more preferably 1000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecyl succinic anhydride, 2- (2 octa- 3-enyl) succinic anhydride, 2- (2,4,6-trimethylnon-3-enyl) succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Chain polycarboxylic acid anhydrides such as
3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride , Norbornene dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2 2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid anhydride, dicyclopentanetetracarboxylic acid diacid Alicyclic polycarboxylic acid anhydrides such as anhydrides;
Phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3'4,4'-diphenylsulfonetetra Carboxylic acid dianhydride, ethylene glycol bis (anhydro trimellitate), glycerin tris (anhydro trimellitate), glycerin bis (anhydro trimellitate) monoacetate, 1,3,3a, 4,5,9b -Aromatic polycarboxylic acid anhydrides such as hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione;
ADEKA HARDNA-EH-700 (trade name (hereinafter the same), manufactured by ADEKA Corporation), Rikacid-HH, same-TH, same-MH, same MH-700 (new Nippon Rika Co., Ltd.), Epikinia 126 Commercial products such as YH-306 and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and chain polyvalent carboxylic acid such as polyvalent carboxylic acid that leads to chain polycarboxylic acid anhydride. acid;
Cycloaliphatic polycarboxylic acids such as cyclohexanedicarboxylic acid, polyvalent carboxylic acids leading to alicyclic polycarboxylic anhydrides;
And aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and polyvalent carboxylic acids that lead to aromatic polyvalent carboxylic acid anhydrides.

  Among them, chain carboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferable because of excellent heat resistance of the cured film, and transparency in the visible light region is particularly difficult to decrease. An acid anhydride is more preferable.

  When the curable resin composition of the present invention contains a polyvalent carboxylic acid (G), the content thereof is 100 parts by mass of the total content of the resin (A) and the (meth) acrylic compound (B). Preferably it is 1-30 mass parts, More preferably, it is 2-20 mass parts, More preferably, it is 2-15 mass parts. When the content of the polyvalent carboxylic acid (G) is within the above range, the cured film is excellent in heat resistance and adhesion.

〔式（１）中、Ｒ^１１は、炭素数１〜２０のアルキル基、フェニル基、ベンジル基又は炭素数２〜５のシアノアルキル基を表す。
Ｒ^１２〜Ｒ^１４は、互いに独立に、水素原子、ハロゲン原子、炭素数１〜２０のアルキル基、フェニル基、ニトロ基又は炭素数１〜２０のアシル基を表し、該アルキル基及び該フェニル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。〕 <Imidazole compound (J)>
The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among these, a compound represented by the formula (2) is preferable.

Wherein ^{(1), R 11} represents an alkyl group, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms having 1 to 20 carbon atoms.
R ^{12 to} R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group The hydrogen atom contained in may be substituted with a hydroxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and heptadecyl group. And an undecyl group.
Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristolyl group, and stearoyl group.

  Examples of the imidazole compound (J) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole. 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxy Methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxy Phenyl) imidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2- Examples include ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

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

<Solvent (E)>
The solvent (E) includes dialkylene glycol dialkyl ether, a solvent (E1), and a solvent (E2).

［式（Ｅ’）中、Ｒ^ｅ１は、炭素数１〜３のアルカンジイル基を表す。
Ｒ^ｅ２及びＲ^ｅ３は、互いに独立に、炭素数１〜４のアルキル基を表す。］
Ｒ^ｅ１のアルカンジイル基としては、メチレン基、エチレン基、プロパン−１，２−ジイル基、プロパン−１，３−ジイル基等が挙げられ、好ましくは、エチレン基又はプロパン−１，２−ジイル基である。
Ｒ^ｅ２及びＲ^ｅ３のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等が挙げられ、好ましくは、メチル基又はエチル基である。
ジアルキレングリコールジアルキルエーテルとしては、例えば、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル等のジエチレングリコールジアルキルエーテル；
ジプロピレングリコールジメチルエーテル及びジプロピレングリコールジエチルエーテル等のジプロピレングリコールジアルキルエーテル；が挙げられる。
中でも、ジアルキレングリコールジアルキルエーテルは、ジエチレングリコールジアルキルエーテルが好ましく、ジエチレングリコールジメチルエーテル又はジエチレングリコールエチルメチルエーテルがより好ましく、ジエチレングリコールエチルメチルエーテルがさらに好ましい。 Dialkylene glycol dialkyl ether is a solvent comprising a compound represented by the formula (E ′).

[In formula (E ′), R ^e1 represents an alkanediyl group having 1 to 3 carbon atoms.
R ^e2 and R ^e3 each independently represent an alkyl group having 1 to 4 carbon atoms. ]
^Examples of the alkanediyl group of R ^e1 include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and the like, and preferably an ethylene group or propane-1,2-diyl group. It is a group.
^Examples of the alkyl group represented by R ^e2 and R ^e3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and a methyl group or an ethyl group is preferable.
Examples of dialkylene glycol dialkyl ethers include diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;
And dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether.
Of these, the dialkylene glycol dialkyl ether is preferably diethylene glycol dialkyl ether, more preferably diethylene glycol dimethyl ether or diethylene glycol ethyl methyl ether, and even more preferably diethylene glycol ethyl methyl ether.

  The solvent (E1) is a solvent which is different from dialkylene glycol dialkyl ether and has an evaporation rate of 40 or more and 100 or less when the evaporation rate of butyl acetate is 100. The evaporation rate of the solvent (E1) is preferably 45 or more and less than 80, and more preferably 50 or more and less than 75.

  In this specification, the evaporation rate refers to the evaporation rate of a solvent that evaporates from a unit area per unit time. The evaporation rate is a sample with respect to the evaporation rate (100) of n-butyl acetate at a temperature of 23 ° C. and a relative humidity of 50%. Expressed as the rate of evaporation of (solvent). A specific measurement method is as follows. In a hood capable of supplying nitrogen gas, a chemical balance and a filter paper No. 2 petri dishes (70 mmφ) with 2 (70 mmφ) were installed, n-butyl acetate was put on one side and 1.0 g each of the sample was put on the other side, and nitrogen gas was supplied into the hood at a flow rate of 30 NL / ml. The weights of n-butyl acetate and the sample were measured at the same time every 60 seconds, and the average value of the evaporation rates calculated from the weights at the time of 60 seconds, 120 seconds and 180 seconds was taken as the evaporation rate of the sample.

Examples of the solvent (E1) include ether solvents such as ethylene glycol monomethyl ether (evaporation rate: 47), propylene glycol monomethyl ether (62), propylene glycol monoethyl ether (46);
Ester solvents such as methyl pyruvate (42) and butyl propionate (45);
Ketone solvents such as 2-heptanone (40);
Aromatic hydrocarbon solvents such as xylene (70);
Examples include alcohol solvents such as 1-butanol (47), 2-butanol (89), and isobutanol (74).
Among these, the solvent (E1) is preferably propylene glycol monomethyl ether or ethylene glycol monomethyl ether, and more preferably propylene glycol monomethyl ether.

The solvent (E2) is a solvent which is different from dialkylene glycol dialkyl ether and has an evaporation rate of 13 or more and less than 40 when the evaporation rate of butyl acetate is 100. The evaporation rate of the solvent (E2) is preferably 25 or more and less than 40, more preferably 30 or more and less than 40.
Examples of the solvent (E2) include ether solvents such as ethylene glycol monoethyl ether (32), ethylene glycol monopropyl ether (20), ethylene glycol monobutyl ether (19), and propylene glycol monopropyl ether (21);
Ester solvents such as methyl lactate (29), ethyl lactate (22), ethyl pyruvate (31);
3-methoxybutyl acetate (14), propylene glycol monomethyl ether acetate (33), propylene glycol monoethyl ether acetate (19), propylene glycol monomethyl ether propionate (19), ethylene glycol monomethyl ether acetate (31), ethylene glycol Ether ester solvents such as monoethyl ether acetate (21) and methyl 3-methoxypropionate (32);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (15), diisobutyl ketone (20), and cyclohexanone (23);
And amide solvents such as N, N-dimethylformamide (17).
Among them, the solvent (E2) is preferably propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, or methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate.

The content of each solvent in the solvent (E) is based on the total amount of the solvent (E).
Dialkylene glycol dialkyl ether; 1-45% by mass
Solvent (E1); 5 to 80% by mass
Solvent (E2); 5 to 80% by mass
Is preferred,
Dialkylene glycol dialkyl ether; 10 to 40% by mass
Solvent (E1); 10-70 mass%
Solvent (E2); 10-70 mass%
Is more preferable.

  The evaporation rate of the solvent (E) as a mixed solvent is preferably 55 or more and 90 or less, more preferably 55 or more and 85 or less, and further preferably 55 or more and 80 or less. The evaporation rate of the solvent (E) can be measured by the above method. When the evaporation rate of the solvent (E) is within the above range, the drying time when drying under reduced pressure is short, and in particular, the flatness of the film obtained by applying the curable resin composition is high.

  Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of the curable resin composition of this invention, More preferably, it is 70-95 mass%. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness of the film obtained by applying the curable resin composition tends to be high.

<Other ingredients>
In the curable resin composition of the present invention, as required, additives such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and the like are added in the technical field. An agent may be contained.

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

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyl Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-a Minopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc. Can be mentioned.

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

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

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

<Method for producing curable resin composition>
The curable resin composition of the present invention includes a resin (A) and a solvent (E), and a (meth) acrylic compound (B), an epoxy resin (C), a polymerization initiator (D), which are used as necessary. Produced by mixing polymerization initiation assistant (D1), antioxidant (F), surfactant (H), polyvalent carboxylic acid (G), imidazole compound (J) and other components by known methods. can do. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Method for producing cured film>
The cured film can be produced by applying the curable resin composition of the present invention on a substrate and curing it by heat.
More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).
Step (1) Step of applying the curable resin composition of the present invention to a substrate Step (2) Step of drying the curable resin composition after coating under reduced pressure to form a composition layer Step (3) Composition layer Heating process

Moreover, when the curable resin composition of this invention contains a polymerization initiator (D), the cured film which has a pattern can be manufactured by performing the following process.
Step (1) Step of applying the curable resin composition of the present invention to a substrate Step (2) Step of drying the curable resin composition after coating under reduced pressure to form a composition layer Step (2a) Composition layer Step (2b) Step of developing the composition layer after exposure Step (3a) Step of heating the composition layer after development

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

Step (2) is a step of forming a composition layer by drying the curable resin composition after coating under reduced pressure. By performing this step, volatile components such as a solvent in the curable resin composition are removed.
The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
Heat drying (pre-baking) may be performed before or after drying under reduced pressure. Heat drying is usually performed using a heating device such as an oven or a hot plate. 30-120 degreeC is preferable and the temperature of heat drying has more preferable 50-110 degreeC. 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 (post-bake) for heating the composition layer. By heating, the composition layer is cured and a cured film is formed. The heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. As the photomask, one having a light-shielding portion corresponding to a portion of the composition layer to be removed is used. The shape of the light shielding part is not particularly limited, and can be selected according to the intended application.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
It is preferable to use an exposure apparatus such as a mask aligner or a stepper because the entire exposure surface can be irradiated with parallel rays uniformly and accurate alignment between the photomask and the composition layer can be performed.

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

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

  The cured film thus obtained has a short required time in the drying process and is excellent in flatness. For example, a color filter substrate used in a liquid crystal display device, an organic EL display device or electronic paper, a touch panel, It is useful as a protective film and overcoat. This makes it possible to manufacture a display device having a high-quality cured film with high productivity.

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をジエチレングリコールエチルメチルエーテル２４０部に溶解させた溶液を、別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤溶液の滴下が終了した後、７０℃で４時間保持し、その後室温まで冷却して、固形分４２．３％の共重合体（樹脂Ａａ）の溶液を得た。得られた樹脂Ａａの重量平均分子量（Ｍｗ）は８０００、分子量分布（Ｍｗ／Ｍｎ）は１．９１、固形分換算の酸価は６０ｍｇ−ＫＯＨ／ｇであった。樹脂Ａａは、下記の構造単位を有する。

Synthesis example 1
Nitrogen was allowed to flow at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 140 parts of diethylene glycol ethyl methyl ether was added and heated to 70 ° C. with stirring. Then 40 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} A solution having 360 parts dissolved in 190 parts of diethylene glycol ethyl methyl ether was prepared, and this solution was dropped into a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was placed in a flask over another 5 hours using another dropping pump. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin Aa) solution having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the molecular weight distribution (Mw / Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH / g. Resin Aa 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: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1 to 6 and Comparative Example 1
<Preparation of curable resin composition>
Each component shown in Table 1 was mixed in the ratio shown in Table 1 to obtain a curable resin composition.

チオール化合物（Ｔ）；ペンタエリスリトールテトラキスプロピオネート（ＰＥＭＰ；ＳＣ有機化学（株）製）
酸化防止剤（Ｆ）；１，３，５−トリス（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルベンジル）−１，３，５−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン（ＩＲＧＡＮＯＸ（登録商標）３１１４；ＢＡＳＦ社製）
多価カルボン酸（Ｇ）；ブタンテトラカルボン酸（リカシッドＢＴ−Ｗ；新日本理化株式会社製）
イミダゾール化合物（Ｊ）；１−ベンジル−２−フェニルイミダゾール（キュアゾール１Ｂ２ＰＺ；四国化成工業（株）製）
界面活性剤（Ｈ）；ポリエーテル変性シリコーンオイル（トーレシリコーンＳＨ８４００；東レ・ダウコーニング（株）製）
溶剤（Ｅ）；Ｅａ；ジエチレングリコールエチルメチルエーテル
溶剤（Ｅ）；Ｅｂ；プロピレングリコールモノメチルエーテル（蒸発速度：６２）
溶剤（Ｅ）；Ｅｃ；プロピレングリコールモノメチルエーテルアセテート（蒸発速度：３３）
溶剤（Ｅ）；Ｅｄ；３−メトキシ−１−ブタノール（蒸発速度：１２）
溶剤（Ｅ）は、硬化性樹脂組成物の固形分量が表１の「固形分量（％）」となるように混合し、溶剤（Ｅ）中の溶剤成分（Ｅａ）〜（Ｅｄ）の値は、溶剤（Ｅ）中の質量比（％）を表す。 In addition, in Table 1, the content part of resin (A) represents the mass part of solid content conversion.
Resin (A); Aa; Resin Aa
(Meth) acrylic compound (B); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin (C); bisphenol A type epoxy resin (JER157S70; manufactured by Mitsubishi Chemical Corporation)
Polymerization initiator (D); Da; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; O-acyloxime compound )
Polymerization initiator (D); Db; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; Hodogaya Chemical ( Co., Ltd .; biimidazole compound)
Polymerization initiation aid (D1); 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline (compound represented by the following formula)

Thiol compound (T); pentaerythritol tetrakispropionate (PEMP; manufactured by SC Organic Chemical Co., Ltd.)
Antioxidant (F); 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trione (IRGANOX (registered trademark) 3114; manufactured by BASF)
Polyvalent carboxylic acid (G); butanetetracarboxylic acid (Licacid BT-W; manufactured by Shin Nippon Chemical Co., Ltd.)
Imidazole compound (J); 1-benzyl-2-phenylimidazole (Curazole 1B2PZ; manufactured by Shikoku Chemicals Co., Ltd.)
Surfactant (H); polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
Solvent (E); Ea; Diethylene glycol ethyl methyl ether Solvent (E); Eb: Propylene glycol monomethyl ether (evaporation rate: 62)
Solvent (E); Ec; Propylene glycol monomethyl ether acetate (evaporation rate: 33)
Solvent (E); Ed; 3-methoxy-1-butanol (evaporation rate: 12)
The solvent (E) is mixed so that the solid content of the curable resin composition is “solid content (%)” in Table 1, and the values of the solvent components (Ea) to (Ed) in the solvent (E) are Represents a mass ratio (%) in the solvent (E).

<Measurement of solvent evaporation rate>
In a hood that can supply nitrogen gas, a chemical balance and a filter paper No. Two petri dishes of 70 mmφ containing 2 (70 mmφ) were placed, and n-butyl acetate was put on one side and 1.0 g of each sample was put on the other side. Nitrogen gas is supplied into the hood at a flow rate of 30 NL / ml, and the weight of n-butyl acetate and the sample is measured simultaneously every 60 seconds. Evaporation rate from the weights after 60 seconds, 120 seconds, and 180 seconds. Was calculated respectively. These average values were used as the evaporation rate of the sample.
Table 2 shows the evaporation rates when the solvent (E) contained in the curable resin compositions of Examples and Comparative Examples was measured as a sample and the evaporation rate of butyl acetate was 100.

<Viscosity measurement>
About the obtained curable resin composition, the viscosity was measured using the viscometer (model; TV-30; Toki Sangyo Co., Ltd. product), respectively. The results are shown in Table 4.

<Measurement of transmittance of composition>
Each of the obtained curable resin compositions was averaged at 400 to 700 nm using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The transmittance (%) was measured. The results are shown in Table 4.

<Production of cured film>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and isopropanol and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 90 ° C. for 10 minutes in a clean oven. Thereafter, post-baking was performed at 230 ° C. for 40 minutes to obtain a cured film.

<Film thickness measurement>
The film thickness of the cured film was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.) with a measurement width of 500 μm and a measurement speed of 10 seconds.

<Measurement of transmittance of cured film>
The obtained cured film was measured for transmittance (%) at 400 nm and average transmittance (%) at 400 to 700 nm using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 4.

<Evaluation of drying time under reduced pressure>
Using a slit die coater (Takada Die-100, manufactured by ITOCHU Corporation) on a 15 cm square ITO film-formed glass substrate, the film thickness after post-baking is 1.5 μm. The coating was performed under various conditions. Thereafter, the time until the degree of vacuum reached 66 Pa was measured with a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) under the conditions of a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25 ° C. A short drying time under reduced pressure is advantageous because the productivity of the cured film increases. The results are shown in Table 4.

<Slit nozzle dryness evaluation>
A condition that the film thickness after post-baking is 1.5 μm on a glass substrate on which a 15 cm square ITO film is formed using a slit die coater (Takada Die-100; manufactured by ITOCHU Corporation). Then, the curable resin composition was applied.
Thereafter, the nozzle of the slit die coater is left as it is for 1 minute, and then the curable resin composition is formed on a glass substrate on which a 15 cm square ITO film is formed in the same manner as described above without washing the tip of the nozzle. Was applied.
The substrate on which the curable resin composition has been applied without washing the tip of the nozzle is dried under reduced pressure with a reduced pressure dryer (VCD Microtech Co., Ltd.) until the degree of reduced pressure reaches 0.5 torr, followed by hot A composition layer was formed by pre-baking on a plate at 90 ° C. for 2 minutes.
After cooling, the surface of the composition layer was illuminated with a Na lamp, and the surface of the composition layer was visually observed.
When the vertical stripe unevenness was clearly confirmed, the mark was ×, when it was slightly confirmed, the mark was △, and when it was not confirmed, the mark was ◯. The results are shown in Table 4.

<Evaluation of flatness; production of evaluation substrate>
Each component shown in Table 3 was mixed in the ratio shown in Table 3 to obtain a colored photosensitive resin composition.

A glass substrate on which a 15 cm square ITO film was formed was washed successively with a neutral detergent, water and isopropanol and then dried. On this board | substrate, the coloring photosensitive resin composition was spin-coated so that the film thickness after a post-baking might be set to 1.6 micrometers. Next, pre-baking was performed at 90 ° C. for 3 minutes in a clean oven to form a colored composition layer. After allowing to cool, the distance between the colored composition layer on the substrate and the quartz glass photomask is set to 100 μm, and the exposure apparatus (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) is used in an atmospheric environment. And was irradiated with light at an exposure amount of 100 mJ / cm ² (based on 365 nm). In addition, this light irradiation performed the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-35; Asahi Techno Glass Co., Ltd. product). As the photomask, a photomask for forming a line and space pattern having a line width of 30 μm was used. The colored composition layer after the light irradiation is developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and then in an oven. Then, post-baking was performed at 220 ° C. for 20 minutes to prepare an evaluation substrate on which a line-and-space coloring pattern having a line width of 30 μm was formed.
When the film thickness of the formed colored pattern was measured, it was confirmed to be 1.6 μm.

<Flatness evaluation 1>
A curable resin composition was applied to the evaluation substrate under the condition that the film thickness after post-baking was 1.5 μm, using a slit die coater (Taku Die-100 manufactured by ITOCHU Corporation). Then, it dried under reduced pressure with the vacuum dryer (made by VCD Microtech Co., Ltd.) until the pressure reduction degree was set to 0.5 torr, and prebaked at 90 degreeC on the hotplate for 2 minutes. After standing to cool, a cured film was formed by post-baking at 230 ° C. for 40 minutes.
Of the cured film on the evaluation substrate, the film thickness was measured at a portion where the colored pattern was not formed under the cured film, and was confirmed to be 1.5 μm.
The height difference of the undulation on the surface of the cured film formed on the colored pattern was measured. If the height difference is 0.5 μm or less, the flatness of the cured film is good, and it can be said that it is particularly useful as a protective film for a color filter. The results are shown in Table 4.

<Flatness evaluation 2>
A curable resin composition was applied to the evaluation substrate under the condition that the film thickness after post-baking was 1.5 μm, using a slit die coater (Taku Die-100 manufactured by ITOCHU Corporation). Then, it dried under reduced pressure with the vacuum dryer (made by VCD Microtech Co., Ltd.) until the pressure reduction degree was set to 0.5 torr, and prebaked at 90 degreeC on the hotplate for 2 minutes. After allowing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp) at an exposure amount of 250 mJ / cm ² (based on 365 nm) in an air atmosphere. In addition, this light irradiation performed the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-31; Asahi Techno Glass Co., Ltd. product). The composition layer after light irradiation was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 60 seconds, washed with water, and then at 230 ° C. A cured film was formed by post-baking for 20 minutes.
Of the cured film on the evaluation substrate, the film thickness was measured at a portion where the colored pattern was not formed under the cured film, and was confirmed to be 1.5 μm.
The height difference of the undulation on the surface of the cured film formed on the colored pattern was measured. If the height difference is 0.5 μm or less, the flatness of the cured film is good, and it can be said that it is particularly useful as a protective film for a color filter. The results are shown in Table 4.

<Resolution evaluation>
Flatness evaluation 2 except that a 2-inch square glass substrate (Eagle XG; manufactured by Corning) was used as the substrate, and light was irradiated with an exposure amount (based on 365 nm) of 100 mJ / cm ² through a photomask during exposure. Similarly, a cured film having a pattern was produced. As a photomask, a mask on which a 20 μm line and space pattern was formed was used.
Using the obtained cured film scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation), the pattern is observed, and if the 20 μm line and space is resolved, it must be resolved. X. The results are shown in Table 4.

  From the results in Table 4, it was confirmed that the curable resin composition of the present invention had a short drying time under reduced pressure and the cured film was excellent in flatness. Therefore, according to the curable resin composition of the present invention, a high-performance cured film can be produced with high productivity.

  ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition with a short drying time at the time of drying under reduced pressure after apply | coating a curable resin composition to a board | substrate can be provided. Since the cured film obtained from the curable resin composition is excellent in flatness, it can be suitably used for a display device or the like.

Claims (5)

Including a curable resin, a (meth) acrylic compound and a solvent,
The curable resin has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A copolymer containing a structural unit derived from a monomer having
The (meth) acrylic compound is a (meth) acrylic compound having three or more (meth) acryloyl groups,
The solvent is a mixed solvent comprising a dialkylene glycol dialkyl ether, a solvent (E1), and a solvent (E2);
The content of dialkylene glycol dialkyl ether is 1% by mass or more and 45% by mass or less based on the total amount of the solvent,
A curable resin composition having a mixed solvent evaporation rate of 55 or more and 90 or less.
Dialkylene glycol dialkyl ether is diethylene glycol ethyl methyl ether,
Solvent (E1): Propylene glycol monomethyl ether, which is different from dialkylene glycol dialkyl ether and has an evaporation rate of 40 or more and 100 or less when the evaporation rate of butyl acetate is 100. Solvent (E2): Propylene glycol monomethyl ether acetate, which is a solvent different from dialkylene glycol dialkyl ether and having an evaporation rate of 13 or more and less than 40 when the evaporation rate of butyl acetate is 100 Furthermore the curable resin composition of claim 1 Symbol mounting comprising an antioxidant. Claim 1 or 2 cured film formed from the curable resin composition. A display device comprising the cured film according to claim 3 . (1) A step of applying the curable resin composition according to claim 1 or 2 to a substrate, (2) a step of drying the curable resin composition after application under reduced pressure to form a composition layer, and (3) The manufacturing method of the cured film including the process of heating a composition layer.