TWI559076B - Curable resin composition - Google Patents

Description

Curable resin composition

The present invention relates to a curable resin composition.

In the display device for liquid crystal display in recent years, a curable resin composition is used in order to form a photo-gap material (PhotoSpacer) and a cured film such as a protective coating layer. As such a curable resin composition, it is known to contain a composition of diethylene glycol ethyl methyl ether and 3-methoxy-1-butanol and propylene glycol monomethyl ether as a solvent (JP2010- 152335A).

Since the curable resin composition which has been proposed in the past is coated with the curable resin composition on the substrate, the drying time at the time of drying under reduced pressure must be long and may not be sufficiently satisfied.

The present invention contains the following invention.

[1] A curable resin composition comprising a curable resin and a solvent, wherein the solvent contains a dialkyl glycol dialkyl ether, a solvent (E1), a solvent (E2), and a dialkyl glycol. The content of the dialkyl ether is from 1% by mass to 45% by mass based on the total amount of the solvent.

Solvent (E1): different from dialkyl glycol dialkyl ether, and evaporation rate is a solvent when the evaporation rate of butyl acetate is taken as 100, and the evaporation rate of solvent (E1) is 40 or more and 100 or less, solvent ( E2): Unlike the dialkyl glycol dialkyl ether, and the evaporation rate is a solvent in which the evaporation rate of the butyl acetate is regarded as 100, the evaporation rate of the solvent (E2) is 13 or more to less than 40.

[2] The curable resin composition according to [1], wherein the curable resin is a structural unit containing at least one selected from the group consisting of a source of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride; A copolymer derived from a structural unit of a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.

[3] The curable resin composition according to [1] or [2] which further contains an antioxidant.

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

[5] A display device comprising the cured film according to [4].

[6] A method for producing a cured film, comprising: (1) a step of coating the curable resin composition according to any one of [1] to [3] on a substrate, and (2) applying the curable resin. The composition is dried under reduced pressure to form a composition layer, and (3) a step of heating the composition layer.

According to the present invention, it is possible to provide a curable resin composition having a short drying time when the curable resin composition is applied onto a substrate and dried under reduced pressure.

[Best Mode for Carrying Out the Invention]

In the present specification, the compounds exemplified as the respective components are not particularly limited, and may be used singly or in combination of plural kinds.

The curable resin composition of the present invention contains a curable resin (hereinafter referred to as "resin (A)") and a solvent (E). The solvent (E) is a dialkyl glycol dialkyl ether, a solvent (E1), and a solvent (E2). The content of the dialkyl glycol dialkyl ether is from 1% by mass to 45% by mass based on the total amount of the solvent.

Solvent (E1): different from dialkyl glycol dialkyl ether, and evaporation rate is a solvent when the evaporation rate of butyl acetate is taken as 100, and the evaporation rate of solvent (E1) is 40 or more and 100 or less, solvent ( E2): Unlike the dialkyl glycol dialkyl ether, and the evaporation rate is a solvent in which the evaporation rate of the butyl acetate is regarded as 100, the evaporation rate of the solvent (E2) is 13 or more to less than 40.

Further, the curable resin composition of the present invention preferably contains at least one selected from the group consisting of at least one selected from the group consisting of an acryloyl group and a methacryl group. (There are compounds called "(meth)acryloyl group)" (hereinafter referred to as "(meth)propene compound (B)"), antioxidant (F), and surfactant (H).

Further, the curable resin composition of the present invention may contain the following At least one component selected from the group consisting of 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 referred to as "epoxy resin" (C)", a polymerization initiator (D), a polymerization initiation aid (D1), a thiol compound (T), at least one selected from the group consisting of a polycarboxylic acid anhydride and a polyvalent carboxylic acid The compound (hereinafter referred to as "polycarboxylic acid (G)") and the imidazole compound (J).

<Resin (A)>

The resin (A) is a curable resin, preferably a thermosetting resin, preferably a resin which is cured by heat of 60 ° C or higher, and a group containing a source of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride. A structural unit selected from at least one of the following (hereinafter referred to as "(a)"), and a monomer derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (hereinafter referred to as The copolymer of the structural unit which is the case of "(b)" is more preferable. Further, the copolymer may have a monomer which can be copolymerized with (a) and derived from a cyclic ether structure having no carbon number of 2 to 4 (hereinafter, referred to as "(c)"). Structural units.

The resin (A) is preferably the following resin "K1" and resin "K2".

Resin "K1": a copolymer of (a) and (b); a resin "K2": a copolymer of (a) and (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, and the like. Zhongkang acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrobenzene An unsaturated carboxylic acid such as formic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexenyl dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2,2,1]hept-2-ene, 5,6-dicarboxybicyclo[2,2,1]heptane- 2-ene, 5-carboxy-5-methylbicyclo[2,2,1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2,2,1]hept-2-ene, 5- A carboxyl group-containing bicyclic unsaturated compound such as carboxy-6-methylbicyclo[2,2,1]hept-2-ene or 5-carboxy-6-ethylbicyclo[2,2,1]hept-2-ene Class; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2 , 3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2,2,1]hept-2-ene anhydrate, etc., unsaturated dicarboxylic acid anhydrous Unsaturation of divalent or higher polycarboxylic acids such as succinic acid mono [2-(methyl) propylene oxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxyethyl] ester Mono[(meth)acryloxyalkyl]esters.

An unsaturated acrylic acid or the like which contains a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, from the viewpoint of solubility in the copolymerization reactivity or the aqueous alkali solution, (meth)acrylic acid and maleic anhydride are preferred, and (meth)acrylic acid is more preferred.

In the present specification, "(meth)acrylonitrile" means at least one selected from the group consisting of an acryloyl group and a methacryloyl group. The expressions "(meth)acrylic acid" and "(meth)acrylate" have the same meaning.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an olefinic unsaturated group. A polymerizable compound of a bond. (b) It is preferred to use a cyclic ether having 2 to 4 carbon atoms and a monomer having a (meth)acryloxy group.

(b), for example, a monomer (b1) having an epoxy group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), an aoxetanyl group and an alkene a monomer (b2) having an unsaturated bond (hereinafter referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3)") situation).

(b1) For example, a case where the unsaturated aliphatic hydrocarbon having a linear or branched chain shape is a monomer (b1-1) having an epoxidized structure (hereinafter referred to as "(b1-1)" And the unsaturated alicyclic hydrocarbon is a monomer (b1-2) having an epoxidized structure (hereinafter referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, and shrinkage. Glyceryl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinyl benzyl 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(glycidyloxy) Styrene, 2,3,4-glycol (glycidyloxymethyl)styrene, 2,3,5-gin (glycidyloxymethyl)styrene, 3,4,5-para (Glycidyloxymethyl)styrene, 2,4,6-gin (glycidyloxymethyl)styrene, and the like.

Examples of the (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.). 3,4-Epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer-A400; manufactured by Diacel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer-M100; Daicel Chemical Industry Co., Ltd.) (1) A compound represented by the formula (11).

[In the formulae (I) and (II), R ^b1 and R ^b2 are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group; X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S-, or * -R ^b3 -NH-. R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms; * is a bond indicating 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 secondary butyl group, and a tertiary butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

As R ^b1 and R ^b2 , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom or a methyl group is more preferable.

As the alkanediyl group, a methylene group, an ethylidene group, a propane-1,2diyl group, a propane-1,3diyl group, a butane-1,4diyl group, a pentane-1,5-diyl group can be exemplified. , hexane-1,6 diyl and the like.

^Preferred examples of X ^b1 and X ^b2 include a single bond, a methylene group, an ethylidene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, more preferably a single bond, and *-CH ₂ CH ₂ -O-. * is a bond indicating the bond with O.

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15). Wherein, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), or the formula (I-11) to the formula (I- 15) The compound shown is preferred. The compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is more preferably.

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Wherein, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), or the formula (II-11) to the formula (II- 15) The compound shown is preferred. A compound represented by the formula (II-1), the formula (II-7), the formula (II-9), or the 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 in combination at any ratio. In the case of mixing, the content of the compound represented by the formula (I) and the compound of the formula (II) is on a molar basis, preferably from 5:95 to 95:5, preferably from 10:90 to 90:10. More preferably, it is 20:80 to 80:20.

As the (b2), an oxetanyl group and a (meth) acryloxy group are more preferable.

Examples of the (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3 -ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Oxyethyl oxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane and the like.

As the (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is preferred. The (b3) may, for example, be tetrahydrofuranyl acrylate (for example, Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) or tetrahydrofuranyl methacrylate.

(b) is preferably (b1) from the viewpoint of high reliability such as heat resistance and chemical resistance of the obtained cured film. Moreover, it is preferable to have (b1-2) from the viewpoint of excellent storage stability of the curable resin composition.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and n-butyl (meth)acrylate may be mentioned. , (butyl) (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate a lipid ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5,2,1,0 ^2.6 ]癸- 8-based (meth) acrylate (in the technical field, the conventional name of "dicyclopentyl (meth) acrylate", and also known as "tricyclodecyl (meth) acrylate) Case.), Tricyclo[5,2,1,0 ^2.6 ]decene-8-yl (meth)acrylate (in the technical field, the use of "dicyclopentenyl (meth)acrylate" The name of the case.), (cyclo) oxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate , propynyl (meth) acrylate, phenyl (meth) acrylate, (A) (meth) acrylate such as naphthyl acrylate or benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (meth) acrylates; 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 - alkene, 5-hydroxymethylbicyclo[2,2,1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2,2,1]hept-2-ene, 5-methoxy Bicyclo[2,2,1]hept-2-ene, 5-ethoxybicyclo[2,2,1]hept-2-ene, 5,6-dihydroxybicyclo[2,2,1]heptane- 2-ene, 5,6-bis(hydroxymethyl)bicyclo[2,2,1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2,2,1]g 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-tris-butoxycarbonylbicyclo[2,2,1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2, 2,1]hept-2-ene, 5-benzene Oxycarbonylbicyclo[2,2,1]hept-2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2,2,1]hept-2-ene, 5,6-bis ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2,2,1]hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl Maleic imine, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide butyrate, N-amber Dicarbonyl such as amino-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl)maleimide Yttrium derivatives; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile , chlorinated ethylene, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butyl Diene, etc.

Among these, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzyl horse are used from the viewpoints of copolymerization reactivity and heat resistance. It is preferred to carry out the imine and bicyclo[2,2,1]hept-2-ene.

In the resin [K1], the ratio of the structural unit derived from the respective monomers is a structural unit derived from (a) with respect to the entire structural unit constituting the resin [K1]: 5 to 60 mol% The structural unit derived from (b): 40 to 95 mol% is ideal, and the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (b): 50 to 90 mol% Better.

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

Resin [K1], for example, can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd.: Chemicals (People's), 1st Edition, 1st Brush, March 1, 1972) It is manufactured by the cited documents described in this document.

Specifically, the quantitative amount, the polymerization initiator, the solvent, and the like of (a) and (b) are placed in a reaction container, for example, by replacing oxygen with nitrogen to form a deoxidizing environment, and heating while stirring The method of insulation. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and can be used as a general user in the field. As the polymerization initiator, for example, an azo compound (2,2'-azobisisobutyronitrile, 2.2'-azo (2,4-dimethylvaleronitrile), etc.) or organic Oxide (benzaldehyde peroxide, etc.). The solvent is not particularly limited as long as it can dissolve each monomer, and examples thereof include a solvent used in the curable resin composition described later.

Further, as the obtained resin, the solution after the reaction may be used as it is, or a solution which has been concentrated or diluted may be used, or a solid (powder) may be taken out by a method such as reprecipitation. In particular, as a polymerization solvent, the solvent used in the curable resin composition of the present invention can be used after the reaction Since the solution is used as it is in the production of the curable resin composition, the production steps of the curable resin composition can be simplified.

In the resin [K2], the ratio derived from the respective structural units is based on the structural unit derived from (a) with respect to the entire structural unit constituting the resin [K2]: 2 to 40 mol% is derived from (b) The structural unit: 2 to 95 mol% of the structural unit derived from (c): 1 to 65 mol% is ideal, and the structural unit derived from (a): 5 to 35 mol% is derived from (b) The structural unit: 5 to 80 mol% derived from the structural unit of (c): 1 to 60 mol% is more preferable.

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 the entire structural unit constituting the resin [K2]. To be more preferably at 90 to 99 mol%.

When the ratio of the structural unit constituting the resin [K2] is within the above range, the storage stability of the curable resin composition tends to be excellent, and the cured film is excellent in chemical resistance, heat resistance, and mechanical strength.

The resin [K2] can be produced by the same method as the resin [K1].

Specific examples of the resin [K1] include a compound represented by (meth)acrylic acid/formula (I-1) (hereinafter, abbreviated as "formula (I-1)". Formula (I-2) Copolymer of (method, etc.), (meth)acrylic acid / copolymer of formula (I-2), (meth)acrylic acid / copolymer of formula (I-3), (meth)acrylic acid / formula ( Copolymer of I-4), (meth)acrylic acid / copolymer of formula (I-5), (meth)acrylic acid / copolymer of formula (I-6), (meth)acrylic acid / Copolymer of the formula (I-7), (meth)acrylic acid / copolymer of the formula (I-8), (meth)acrylic acid / copolymer of the formula (I-9), (meth)acrylic acid / formula ( Copolymer of I-10), (meth)acrylic acid / copolymer of formula (I-11), (meth)acrylic acid / copolymer of formula (I-12), (meth)acrylic acid / formula (I- 13) copolymer, (meth)acrylic acid / copolymer of formula (I-14), (meth)acrylic acid / copolymer of formula (I-15), (meth)acrylic acid / formula (II-1) Copolymer, (meth)acrylic acid / copolymer of formula (II-2), (meth)acrylic acid / copolymer of formula (II-3), copolymerization of (meth)acrylic acid / 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 the formula (II-8), (meth)acrylic acid / copolymer of the formula (II-9), (meth)acrylic acid / copolymer of the formula (II-10), (A) Acrylic acid / copolymer of formula (II-11), (meth)acrylic acid / copolymer of formula (II-12), (meth)acrylic acid / copolymer of formula (II-13), (methyl) Acrylic acid / copolymer of formula (II-14), (meth)acrylic acid / copolymer of formula (II-15), (methyl Acrylic acid / copolymer of formula (I-1) / formula (II-1), (meth)acrylic acid / copolymer of formula (I-2) / formula (II-2), (meth)acrylic acid / (I-3) / copolymer of the formula (II-3), (meth)acrylic acid / copolymer of the formula (I-4) / formula (II-4), (meth)acrylic acid / formula (I-5) Copolymer of formula (II-5), (meth)acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth)acrylic acid / formula (I-7) / formula ( Copolymer of II-7), (meth)acrylic acid / copolymer of formula (I-8) / formula (II-8), (meth)acrylic acid / formula (I-9) / formula (II-9) Copolymer, (meth)acrylic acid / copolymer of formula (I-10) / formula (II-10), (meth)acrylic acid / copolymer of formula (I-11) / formula (II-11), (Meth)acrylic acid / copolymer of formula (I-12) / formula (II-12), (meth)acrylic acid / copolymer of formula (I-13) / formula (II-13), (methyl) Acrylic acid / (I-14) / copolymer of formula (II-14), (meth)acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth)acrylic acid / formula (I -1) / copolymer of the formula (I-7), (meth)acrylic acid / copolymer of the formula (I-1) / formula (II-7), crotonic acid / copolymer of the formula (I-1), Crotonic acid / copolymer of formula (I-2), copolymer of crotonic acid / formula (I-3), crotonic acid / formula (I-4) Polymer, crotonic acid / copolymer of formula (I-5), crotonic acid / copolymer of formula (I-6), crotonic acid / copolymer of formula (I-7), crotonic acid / formula (I-8 Copolymer, crotonic acid / copolymer of formula (I-9), crotonic acid / copolymer of formula (I-10), crotonic acid / copolymer of formula (I-11), crotonic acid / formula (I -12) copolymer, crotonic acid / copolymer of formula (I-13), crotonic acid / copolymer of formula (I-14), crotonic acid / copolymer of formula (I-15), crotonic acid / formula (II-1) copolymer, crotonic acid / copolymer of formula (II-2), crotonic acid / copolymer of formula (II-3), crotonic acid / copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / copolymer of formula (II-6), crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), Crotonic acid / copolymer of formula (II-9), copolymer of crotonic acid / formula (II-10), copolymer of crotonic acid / formula (II-11), copolymerization of crotonic acid / formula (II-12) , crotonic acid / copolymer of formula (II-13), crotonic acid / copolymer of formula (II-14), crotonic acid / copolymer of formula (II-15), maleic acid / formula (I-1 Copolymer, maleic acid / copolymer of formula (I-2), maleic acid / copolymer of formula (I-3), Malay / copolymer of formula (I-4), copolymer of maleic acid / formula (I-5), copolymer of maleic acid / formula (I-6), maleic acid / formula (I-7) Copolymer, maleic acid / copolymer of formula (I-8), copolymer of maleic acid / formula (I-9), copolymer of maleic acid / formula (I-10), maleic acid / formula Copolymer of (I-11), copolymer of maleic acid/formula (I-12), copolymer of maleic acid/formula (I-13), copolymer of maleic acid/formula (I-14) , maleic acid / copolymer of formula (I-15), copolymer of maleic acid / formula (II-1), copolymer of maleic acid / formula (II-2), maleic acid / formula (II -3) copolymer, maleic acid / copolymer of formula (II-4), copolymer of maleic acid / formula (II-5), copolymer of maleic acid / formula (II-6), horse Copolymer / copolymer of formula (II-7), copolymer of maleic acid / formula (II-8), copolymer of maleic acid / formula (II-9), maleic acid / formula (II-10) Copolymer, maleic acid / copolymer of formula (II-11), copolymer of maleic acid / formula (II-12), copolymer of maleic acid / formula (II-13), maleic acid / copolymer of formula (II-14), copolymer of maleic acid / formula (II-15), (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1), (meth)acrylic acid /maleic anhydride / type (I-2) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-3), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-4), Methyl)acrylic acid/maleic anhydride/copolymer of formula (I-5), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-6), (meth)acrylic acid/maleic anhydride/form (I-7) copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-8), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-9), Methyl)acrylic anhydride/maleic anhydride/copolymer of formula (I-10), (meth)acrylic acid/maleic anhydride/copolymer of formula (I-11), (meth)acrylic acid/maleic anhydride/ a copolymer of the formula (I-12), a copolymer of (meth)acrylic acid/maleic anhydride/formula (I-13), a copolymer of (meth)acrylic acid/maleic anhydride/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/ a copolymer of the formula (II-2), a copolymer of (meth)acrylic acid/maleic anhydride/formula (II-3), a copolymer of (meth)acrylic acid/maleic anhydride/formula (II-4), Copolymerization of (meth)acrylic acid/maleic anhydride/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/malay Anhydride/copolymer of formula (II-8), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-9), copolymerization of (meth)acrylic acid/maleic anhydride/formula (II-10) , (meth)acrylic acid/maleic anhydride/copolymer of formula (II-11), (meth)acrylic acid/maleic anhydride/copolymer of formula (II-12), (meth)acrylic acid/Malay Anhydride/copolymer of formula (II-13), copolymer of (meth)acrylic acid/maleic anhydride/formula (II-14), copolymerization of (meth)acrylic acid/maleic anhydride/formula (II-15) Things and so on.

Specific examples of the resin [K2] include (meth)acrylic acid/copolymer of the formula (I-1)/methyl (meth)acrylate, and (meth)acrylic acid/form (I-2). / (meth)acrylic acid methyl ester copolymer, (meth)acrylic acid / copolymer of formula (I-3) / (meth)acrylic acid methyl ester, (meth)acrylic acid / formula (I Copolymerization of -4)/(meth)acrylic acid methyl ester copolymer, (meth)acrylic acid/(I-5)/(meth)acrylic acid methyl ester , (meth)acrylic acid / copolymer of methyl (I-6) / (meth) acrylate, (meth) acrylate / methyl (I-7) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of methyl (I-8) / (meth) acrylate, (meth) acrylate / methyl (I-9) / (meth) acrylate Copolymer of ester, (meth)acrylic acid / copolymer of methyl (I-10) / methyl (meth)acrylate, (meth)acrylic / formula (I-11) / (meth)acrylic acid Copolymer of methyl ester, (meth)acrylic acid / copolymer of methyl (I-12) / methyl (meth)acrylate, (meth) acrylic / formula (I-13) / (methyl a copolymer of methyl acrylate, a copolymer of (meth)acrylic acid / methyl (I-14) / methyl (meth) acrylate, (meth) acrylic / formula (I-15) / ( Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylate / methyl (II-1) / methyl (meth) acrylate, (meth) acrylate / formula (II-2) / (meth)acrylic acid methyl ester copolymer, (meth)acrylic acid / copolymer of formula (II-3) / (meth)acrylic acid methyl ester, (meth)acrylic acid / formula (II- 4) / (methyl) acrylate methyl ester Compound, (meth)acrylic acid / copolymer of methyl (II-5) / methyl (meth)acrylate, (meth)acrylic acid / methyl (II-6) / methyl (meth)acrylate Copolymer, (meth)acrylic acid / copolymer of formula (II-7) / methyl (meth) acrylate, (meth) acrylate / formula (II-8) / (meth) acrylate Copolymer of base ester, (meth)acrylic acid / copolymer of methyl (II-9) / methyl (meth)acrylate, (meth)acrylic acid / formula (II-10) / (methyl) Copolymer of methyl acrylate, (meth)acrylic acid / copolymer of methyl (II-11) / methyl (meth) acrylate, (meth) acrylate / formula (II-12) / (A Co-polymer of methyl acrylate, (meth)acrylic acid / copolymer of methyl (II-13) / methyl (meth) acrylate, (meth) acrylate / formula (II-14) / Copolymer of methyl (meth) acrylate, copolymer of (meth) acrylate / methyl (II-15) / methyl (meth) acrylate, (meth) acrylate / formula (I-1 Copolymer of /(meth)acrylic acid dicyclopentyl ester, (meth)acrylic acid /copolymer of formula (II-1)/dicyclopentyl (meth)acrylate, (meth)acrylic acid /Formula (I-1) / Formula (II-1) / (A a copolymer of dicyclopentyl acrylate, a copolymer of crotonic acid / dicyclopentyl (I-1) / (meth) acrylate, maleic acid / formula (I-1) / ( Copolymer of dicyclopentyl methyl methacrylate, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1) / dicyclopentyl (meth) acrylate, (methyl) Acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / dicyclopentyl (meth) acrylate, crotonic acid / bicyclic ring of formula (II-1) / (meth) acrylate Copolymer of amyl ester, maleic acid / copolymer of formula (II-1) / dicyclopentyl (meth) acrylate, (meth)acrylic acid / maleic anhydride / formula (II-1) /Copolymer of dicyclopentyl (meth) acrylate, (meth)acrylic acid / methyl (II-1) / methyl (meth) acrylate / dicyclopentyl (meth) acrylate Polymer, (meth)acrylic acid / copolymer of phenyl (I-1) / phenyl (meth) acrylate, (meth) acrylate / phenyl (II-1) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / phenyl (meth) acrylate, crotonic acid / formula (I-1) / (A Co-polymer of phenyl acrylate Maleic acid / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / phenyl ester of formula (I-1) / (meth) acrylate Copolymer, (meth)acrylic acid / copolymer of formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, crotonic acid / formula (II-1) / ( Copolymer of phenyl methacrylate, copolymer of maleic acid / phenyl (II-1) / phenyl (meth) acrylate, (meth) acrylate / maleic anhydride / formula (II- 1) / co-polymer of phenyl (meth) acrylate, (meth) acrylate / copolymer of formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate , (meth)acrylic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / copolymer of formula (II-1) / diethyl maleate, ( Methyl)acrylic acid / copolymer of formula (I-1) / formula (II-1) / diethyl maleate, co-polymer of crotonic acid / formula (I-1) / diethyl maleate , maleic acid / copolymer of formula (I-1) / diethyl maleate, (meth)acrylic acid / maleic anhydride / copolymer of formula (I-1) / diethyl maleate , (meth)acrylic acid / methyl (I-1) / (meth) acrylate / Diethyl maleate Copolymer, crotonic acid / copolymer of formula (II-1) / diethyl maleate, maleic acid / copolymer of formula (II-1) / diethyl maleate, (a Acrylic acid/maleic anhydride/copolymer of formula (II-1)/diethyl maleate, (meth)acrylic acid/methyl (II-1)/methyl (meth)acrylate/Malay Copolymer of diethyl acid, (meth)acrylic acid / copolymer of 2-hydroxyethyl (I-1) / (meth) acrylate, (meth) acrylic / formula (II-1) /co-polymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / of 2-hydroxyethyl (I-1) / (II-1) / 2-hydroxyethyl (meth)acrylate Polymer, crotonic acid / copolymer of 2-hydroxyethyl (I-1) / (meth) acrylate, maleic acid / 2-hydroxyethyl (I-1) / (meth) acrylate Ester copolymer, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/form (I-1 a copolymer of methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid / 2-hydroxyethyl (II-1) / (meth) acrylate Polymer, maleic acid / 2-hydroxyl (II-1) / (meth) acrylate Co-polymer of ethyl ethyl ester, (meth)acrylic acid / maleic anhydride / copolymer of formula (II-1) / 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid / II-1)/(meth)acrylic acid methyl ester/co-polymer of 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid/(I-1)/bicyclo[2,2,1 a copolymer of hept-2-ene, (meth)acrylic acid/copolymer of formula (II-1)/bicyclo[2,2,1]hept-2-ene, (meth)acrylic acid/form ( I-1) / formula (II-1) / bicyclo [2, 2, 1] hept-2-ene copolymer, crotonic acid / formula (I-1) / bicyclo [2, 2, 1] g 2-alkenyl copolymer, maleic acid / copolymer of formula (I-1) / bicyclo [2,2,1]hept-2-ene, (meth)acrylic acid / maleic anhydride / formula (I -1)/bicyclo[2,2,1]hept-2-ene copolymer, (meth)acrylic acid/(I-1)/methyl(meth)acrylate/bicyclo[2,2, 1] co-polymer of hept-2-ene, crotonic acid / copolymer of formula (II-1) / bicyclo [2, 2, 1] hept-2-ene, maleic acid / formula (II-1) /bicyclo[2,2,1]hept-2-ene copolymer, (meth)acrylic acid/maleic anhydride/(II-1)/bicyclo[2,2,1]hept-2-ene Copolymer, (meth)acrylic acid / formula (II-1) / (meth) acrylic acid a copolymer of a base ester/bicyclo[2,2,1]hept-2-ene, a (meth)acrylic acid/copolymer of the formula (I-1)/N-cyclohexylmaleimide, (a) Acrylic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide, (meth)acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexyl horse Copolymer of quinone imine, crotonic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide, maleic acid / formula (I-1) / N-cyclohexylmalay Copolymer of quinone imine, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/N-cyclohexylmaleimide, (meth)acrylic acid/form (I-1 / (meth)acrylic acid methyl ester / N-cyclohexyl maleimide copolymer, crotonic acid / copolymer of formula (II-1) / N-cyclohexyl maleimide, horse Co-polymer of acid/(II-1)/N-cyclohexylmaleimide, (meth)acrylic acid/maleic anhydride/(II-1)/N-cyclohexylmaleimide Copolymer, (meth)acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, (meth) acrylate / formula (I -1) / copolymer of styrene, (meth)acrylic acid / copolymer of formula (II-1) / styrene, (Meth)acrylic acid / copolymer of formula (I-1) / formula (II-1) / styrene, crotonic acid / copolymer of formula (I-1) / styrene, maleic acid / formula ( I-1)/copolymer of styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (I-1)/styrene, (meth)acrylic acid/formula (I-1)/( a copolymer of methyl methacrylate/styrene, a crotonic acid/copolymer of formula (II-1)/styrene, a copolymer of maleic acid/formula (II-1)/styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/styrene, (meth)acrylic acid/complex of formula (II-1)/methyl (meth)acrylate/styrene Polymer, (meth)acrylic acid / copolymer of formula (I-1) / N-cyclohexylmaleimide / styrene, (meth)acrylic acid / formula (II-1) / N-cyclohexyl a copolymer of maleic imine/styrene, a copolymer of (meth)acrylic acid/(I-1)/(II-1)/N-cyclohexylmaleimide/styrene, Crotonic acid/copolymer of formula (I-1)/N-cyclohexylmaleimide/styrene, maleic acid/(I-1)/N-cyclohexylmaleimide/styrene Copolymer, (meth)acrylic acid / maleic anhydride / formula (I-1)/N-cyclohexylmaleimide/styrene copolymer, (meth)acrylic acid/(I-1)/(meth)acrylic acid methyl ester/N-cyclohexyl horse Copolymer of bismuth imine/styrene, crotonic acid / copolymer of formula (II-1) / N-cyclohexylmaleimide / styrene, maleic acid / formula (II-1) / Copolymer of N-cyclohexylmaleimide/styrene, (meth)acrylic acid/maleic anhydride/copolymer of formula (II-1)/N-cyclohexylmaleimide/styrene (meth)acrylic acid / methyl (II-1) / (meth) acrylate / N-cyclohexyl maleimide / styrene copolymer.

The polystyrene-equivalent weight average molecular weight of the resin (A) is desirably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, particularly preferably 5,000 to 10,000. When the weight average molecular weight of the resin (A) is within the above range, the coatability 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 desirably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the obtained cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mg-KOH/g or more and 180 mg-KOH/g or less, preferably 40 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 50 mg-KOH/g. Above and below 135 mg-KOH/g.

Here, the acid value is a value which is measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be determined by titration using a potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the adhesion between the obtained cured film and the substrate tends to be excellent.

The content of the resin (A) is preferably from 30 to 90% by mass, preferably from 35 to 80% by mass, more preferably from 40 to 70% by mass, based on the solid content of the curable resin composition of the present invention. When the content of the resin (A) is within the aforementioned range, The cured film obtained is excellent in heat resistance, and has a tendency to be excellent in adhesion to a substrate and chemical resistance. Here, the solid content of the curable resin composition means that the total amount of the curable resin composition of the present invention is the amount remaining in the solvent (E).

<(Meth)acrylic compound (B)>

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

Examples of the (meth)acrylic compound (B) having one (meth)acryl fluorenyl group are the same as those exemplified as the above-mentioned (a), (b), and (c). (Meth) acrylates are preferred.

Examples of the (meth)acrylic compound having two (meth)acrylonyl groups include 1,3-butanediol di(meth)acrylate and 1,3-butanediol (methyl). Acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, Ethoxylated bisphenol A di(meth) acrylate, propoxylated neopentyl glycol di(meth) acrylate, ethoxylated neopentyl glycol di(meth) acrylate, 3-methyl Pentyl glycol di(meth)acrylate or the like.

Examples of the (meth)acrylic compound having three (meth)acrylinyl groups include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and ginseng (2- Hydroxyethyl)isocyanate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra ( Methyl) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (methyl) Acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate Reaction of an ester with an acid anhydride, a reaction of dipentaerythritol penta (meth) acrylate with an acid anhydride, a reaction of a tripentaerythritol hepta (meth) acrylate with an acid anhydride, and a caprolactone modified trimethylolpropane tris (a Acrylate, caprolactone modified pentaerythritol tri(meth) acrylate, caprolactone modified ginseng (2-hydroxyethyl) isocyanate tri(meth) acrylate, caprolactone modified pentaerythritol tetra (a) Acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, Caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified trimellititol hexa(meth) acrylate, caprolactone modified tripellitate pentoxide (meth) acrylate, caprolactone modification Tripentaerythritol octa (meth) acrylate, caprolactone Reacting a reaction of pentaerythritol tri(meth) acrylate with an acid anhydride, a reaction of caprolactone-modified dipentaerythritol penta (meth) acrylate with an acid anhydride, and caprolactone-modified trimellititol seven (meth) acrylate A reactant with an acid anhydride or the like.

As the (meth)acrylic compound (B), a (meth)acrylic compound having three or more (meth)acrylonyl groups is preferred, and dipentaerythritol hexa(meth)acrylate is more preferred.

In the case where the curable resin composition of the present invention contains the (meth)acrylic compound (B), the content thereof is preferably 20 to 100 parts by mass, more preferably 100 parts by mass based on the content of the resin (A). It is 25 to 70 parts by mass. When the content of the (meth)acrylic compound (B) is within the above range, the chemical resistance and mechanical strength of the cured film obtained tend to be improved.

<Epoxy Resin (C)>

The epoxy resin (C) is not particularly limited as long as it has a structure different from that of the resin (A), and is selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin. At least one of the groups is ideal.

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure and can be synthesized by reacting with a phenol or a polyhydric alcohol or the like.

Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, and o-cresol. Phenolic epoxy resin and parahydroxyphenylmethane epoxy resin.

The glycidyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure, and can be 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 a glycidyl ester type epoxy resin derived from an aromatic carboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid or terephthalic acid.

The epoxy resin (C) used in the curable resin composition of the present invention is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and an o-cresol novolac type ring. A glycidyl ether type epoxy resin such as an oxygen resin or a polyphenol type epoxy resin is preferable, and among them, a bisphenol A type epoxy resin is particularly preferable.

The glycidyl ether type epoxy resin described above can be synthesized by condensation of a corresponding phenol and epichlorohydrin in the presence of a strong base by a conventionally known method. The related reaction can be carried out by a method known to those skilled in the art. Further, a commercially available product can also be used. As a commercial product of bisphenol A type epoxy resin, JER157S70, EPICOAT 1001, EPICOAT 1002 can be cited. EPICOAT 1003, EPICOAT 1004, EPICOAT 1007, EPICOAT 1009, EPICOAT 1010, EPICOAT 828 (manufactured by Mitsubishi Chemical Corporation). The commercially available product of the bisphenol F-type epoxy resin may, for example, be EPICOAT 807 (manufactured by Mitsubishi Chemical Corporation) or YDF-170 (manufactured by Tohto Kasei Co., Ltd.). As a commercial product of the phenol novolak type epoxy resin, EPICOAT 152, EPICOAT 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, EPPN-202 (manufactured by Nippon Kayaku Co., Ltd.), DEN-438 (manufactured by The Dow Chemical Company) and the like. As a commercial product of the o-cresol novolac type epoxy resin, EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.) can be cited. )Wait. As a commercial item of the 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 from 100 to 500 g/eq, more preferably from 150 to 400 g/eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per one epoxy group. The epoxy equivalent can be measured, for example, according to the method specified in JIS K7236.

The acid value of the epoxy resin (C) is usually less than 30 mg-KOH/g, preferably 10 mg-KOH/g or less.

Further, the weight average molecular weight of the epoxy resin (C) is desirably from 300 to 10,000, preferably from 400 to 6,000, more preferably from 500 to 4,800.

When the curable resin composition of the present invention contains the epoxy resin (C), the content thereof is preferably 100 parts by mass based on the total content of the resin (A) and the (meth)acrylic compound (B). It is 1 to 60 parts by mass, more preferably 5 to 50 parts by mass. When the content of the epoxy resin (C) is within the above range, the adhesion between the obtained cured film and the substrate tends to be excellent.

<Polymerization initiator (D)>

The polymerization initiator (D) is a compound which can generate a living radical, oxygen, or the like by light or heat, and is not particularly limited as long as it can start polymerization, and a known polymerization initiator can be used.

The polymerization initiator (D) is at least one selected from the group consisting of an O-mercaptopurine compound, an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, and a biimidazole compound. A polymerization initiator is preferred, and a polymerization initiator containing an O-fluorenyl ruthenium compound is more preferred. When such a polymerization initiator is used, it is highly sensitive, and the transmittance tends to be high in the visible light region.

The O-mercaptopurine compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * is a binding bond.

As the O-mercaptopurine compound, for example, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoic acid can be cited.醯oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3 -cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazole-3- Ethyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxo Heterocyclic amylmethyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-( 2-methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Irgacure (registered trademark) OXE 01, OXE 02 (above, BASF) A product such as N-1919 (made by Adeka Co., Ltd.).

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 some of these structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by the formula (d2), 2-methyl-2-N-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2 -Dimethylamino-1-(4-N-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methyl) Phenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used. Further, as disclosed in Japanese Laid-Open Patent Publication No. 2002-544205, a polymerization initiator having a group which causes chain movement can also be used.

As a compound having a partial structure represented by the formula (d3), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone and benzyldimethylketal.

From the viewpoint of sensitivity, as the alkylphenone compound, a partially structural compound represented by the formula (d2) is preferred.

As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis ( Trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-anthraquinone-1,3,5 - triazine, 2,4-double (three Chloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran) -2-yl)vinyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5 Triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine.

Examples of the mercaptophosphine compound include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and the like. Commercial products such as Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can also be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-double (2 -Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4, 4 The phenyl group at the ', 5, 5'-position is a biimidazole compound substituted with a carbamoyloxy group (for example, refer to JPH07-10913-A, etc.).

Further, examples of the polymerization initiator (D) include benzene, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether. Occasion compound; benzophenone, methyl o-benzylidene benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ',4,4'-tetrakis (tertiary-butyl peroxide carbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenones; 9,10-phenanthrenequinone An anthraquinone compound such as 2-ethylhydrazine or camphorquinone; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, and a titanocene compound. These are It is preferably used in combination with a polymerization starting aid (D1) (especially an amine) to be described later.

As the polymerization initiator (D), an oxygen generating agent can also be used.

Examples of the oxygen generator include 4-hydroxyphenyldimethylpyridinium-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenylene. Dimethyl 鋶 p-toluene sulfonate, 4-ethyl methoxy phenyl. methyl. Benzoe hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate a salt such as a salt, or a nitrobenzyl tosylate or a benzoin tosylate.

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

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is used together with the polymerization initiator (D) to promote a polymerizable compound (for example, a (meth)acrylic compound (B) which starts polymerization by the polymerization initiator (D). )) a polymerized compound, or a sensitizer.

Examples of the polymerization initiator (D1) include a thiazoline compound, an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the thiazoline compound include a compound represented by the formula (III-1) to the formula (III-3), a compound described in JP2008-65319-A, and the like.

As the amine compound, there may be mentioned: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl benzoic acid benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like is preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

As the alkyl hydrazine compound, there may be mentioned: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, and methylethylphenylthioacetic acid. Dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

In the case where the curable resin composition of the present invention contains the polymerization initiation aid (D1), the content thereof is 100 parts by mass based on the total content of the resin (A) and the (meth)acrylic compound (B). It is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass. When the content of the polymerization initiation aid (D1) is within the above range, the pattern tends to be highly sensitive when the pattern is formed.

<thiol compound (T)>

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

Examples of the thiol compound (T) include hexane dithiol, decane dithiol, 1,4-bis(methylindenyl)benzene, butanediol bis(3-mercaptopropionate), and Butanediol bis(3-mercaptoacetate), ethylene glycol bis(3-mercaptoacetate), trimethylolpropane ginseng (3-mercaptoacetate), butanediol bis(3-mercaptopropane) Acid ester), trimethylolpropane ginseng (3-mercaptopropionate), trimethylolpropane ginseng (3-mercaptoacetate), pentaerythritol bismuth (3-mercaptopropionate), pentaerythritol bismuth (3- Mercaptoacetate), hydroxyethyl ginseng (3-mercaptoacetate), pentaerythritol ruthenium (3-mercaptobutyrate), and 1,4-bis(3-mercaptobutoxy)butane.

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

<Antioxidant (F)>

Examples of the antioxidant (F) include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Among them, a phenolic antioxidant is preferred from the viewpoint of less coloration of the cured film.

Examples of the phenolic antioxidant include 2-tributylbutyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate. 2-[1-(2-hydroxy-3,5-di-tri-pentylphenyl)ethyl]-4,6-di-tert-butylphenyl acrylate, 3,9-bis[2] -{3-(3-Tris-butyl-4-hydroxy-5-methylphenyl)propenyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxy Heterospiro[5,5]undecane, 2,2'-methylenebis(6-tributyl-4-methylphenol), 4,4'-butylene bis(6-tertiary butyl) -3-methylphenol), 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tris-butyl-4-methyl) Phenol), 1,3,5-gin (3,5-di-tri-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H Triketone, 3,3',3",5,5',5"-hexa-tertiary butyl-a,a',a"-(mesityl-2,4,6-triyl) Tri-p-cresol, pentaerythritol bismuth [3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], 2,6-di-tributyl-4-methyl Phenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tertiary butyl-dibenzo[ d, f] {1, 3, 2} dioxaphospholane.

As a phenolic antioxidant, a commercially available product may be used, and as a commercially available phenolic antioxidant, for example, SUMILIZER (registered trademark) BHT, GM, GS, and GP (all of which are Sumitomo Chemical Co., Ltd.) )), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all of which are manufactured by BASF Corporation).

As a sulfur-based antioxidant, for example, a 3,3'-thio group can be cited. Dilauryl dipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and barium pentaerythritol (3-lauryl sulfur) Propionate). As a sulfur-based antioxidant, a commercially available product may be used, and as a commercially available sulfur-based antioxidant, for example, SUMILIZER (registered trademark) TPL-R, TP-D (all of which are Sumitomo Chemical Co., Ltd.) )system).

Examples of the phosphorus-based antioxidant include trioctyl phosphate, tris(dodecyl) phosphate, tridecyl phosphate, decylphenyl phosphate, and distearyl pentylenetetraol. Diphosphate, and tetrakis(trimethyl)-1,1,3-glycol(2-methyl-5-tributyl-4-hydroxyphenyl)butane diphosphate. As a phosphorus-based antioxidant, a commercially available product may be used, and as a commercially available phosphorus-based antioxidant, for example, IRGAFOS (registered trademark) 168, 12, and 38 (all of which are manufactured by BASF Corporation) may be mentioned. ADK STAB 329K and ADK STAB PE36 (all above, all made by ADEKA).

Examples of the amine-based antioxidant include N,N'-di-secondary butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, and N. , N'-di-cyclohexyl-p-phenylenediamine, N,N'-di-phenyl-p-phenylenediamine, and N,N'-bis(2-naphthyl)-p-stretch Phenylenediamine. As the above-mentioned amine-based antioxidant, a commercial product may be used, and as a commercially available amine-based antioxidant, for example, SUMILIZER (registered trademark) BPA, BPA-M1, and 4ML (above, all of Sumitomo Chemical ( Stock system)).

When the curable resin composition of the present invention contains the antioxidant (F), the content thereof is preferably 100 parts by mass based on the total content of the resin (A) and the (meth)acrylic compound (B). 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the heat resistance and pencil hardness of the obtained cured film tend to be excellent.

<Interacting Agent (H)>

Examples of the surfactant (H) include a ruthenium-based surfactant, a fluorine-based surfactant, and a ruthenium-based surfactant having a fluorine atom.

As the oxime-based surfactant, a surfactant having a siloxane coupling is exemplified.

Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Emu Oil SH8400 (trade name; Toray Dow Corning) System), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF 4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japanese contract company system) and so on.

As a fluorine-containing surfactant, a surfactant of a fluorocarbon chain is mentioned.

Specific examples include Fluorinert (registered trademark) FC430, Fluorinert FC 431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, and MEGAFAC F552. MEGAFAC F553, MEGAFAC F554, MEGAFAC F555, MEGAFAC F556, MEGAFAC F558, MEGAFAC F559, MEGAFAC R30 (made by DIC), FTOP (registered trademark) EF301, FTOP EF303, FTOP EF351, FTOP EF352 (Mitsubishi Materials Electronics Co., Ltd. )), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (made by Asahi Glass Co., Ltd.), E5844 (Daikin fine chemical) Research institute system (share) system, etc.

Examples of the oxime-based surfactant having a fluorine atom include a surfactant of a siloxane coupling and a fluorocarbon chain, and specific examples thereof include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, and MEGAFAC F477. , MEGAFAC F443 (DIC (share) system) and so on. Ideally, MEGAFAC (registered trademark) F475 can be cited.

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

<polyvalent carboxylic acid (G)>

The polyvalent carboxylic acid (G) is a compound selected from the group consisting of a polyvalent carboxylic anhydride and a polyvalent carboxylic acid. The polyvalent carboxylic acid means a compound having two or more carboxyl groups, and the polyvalent carboxylic anhydride means an anhydrous substance of a polyvalent carboxylic acid. The polyvalent carboxylic acid (G) is preferably a molecular weight of 3,000 or less, more preferably 1,000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, and 2-(2-oct-3). -alkenyl)succinic anhydride, 2-(2,4,6-trimethylindol-3-enyl) succinic anhydride, tricarbary anhydride, 1,2,3,4-butane tetracarboxylate Chain polyvalent carboxylic anhydride such as acid dianhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride , hexahydrophthalic anhydride, 4-methylhexahydrophthalic acid Anhydride, norbornene dicarboxylic anhydride, methyl bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, bicyclo [2,2,1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic anhydride, cyclopentane tetracarboxylate An alicyclic polyvalent carboxylic anhydride such as acid dianhydride; phthalic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid Desic anhydride, 3,3',4,4'-diphenylsulfotetracarboxylic dianhydride, ethylene glycol bis(hydrogen trimellitate), glycerol (dehydrated trimellitate), glycerin double (dehydrated trimellitate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxa-3-furanyl)naphtho[ 1,2,-c] an aromatic polyvalent carboxylic anhydride such as furan-1,3-dione;

It is also possible to use: Adeka Hardner EH-700 (trade name (same as below), ADEKA Co., Ltd.), Rikacid-HH, Rikacid-TH, Rikacid-MH, Rikacid MH-700 (Nippon Chemical and Chemical Co., Ltd.), Commercial products such as Epicure 126, Epicure YH-306, and Epicure DX-126 (oiled SHELL EOPXY).

Examples of the polyvalent carboxylic acid include chain-like polyoxalates such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and a chain-like polyvalent carboxylic acid anhydride. a carboxylic acid; a cyclohexane dicarboxylic acid; an alicyclic polyvalent carboxylic acid such as a polyvalent carboxylic acid derived from an alicyclic polyvalent carboxylic anhydride; isophthalic acid, terephthalic acid, 1, 4, 5, 8 - naphthalenetetracarboxylic acid, an aromatic polyvalent carboxylic acid derived from a polyvalent carboxylic acid of an aromatic polyvalent carboxylic anhydride;

Among them, from the viewpoint of excellent heat resistance of the cured film, particularly in view of the fact that the transparency in the visible light region is not easily lowered, chain carboxylic anhydride and alicyclic polyvalent carboxylic anhydride are preferred, and alicyclic polyvalent carboxylic anhydride is used. Better.

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

<Imidazole compound (J)>

The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole backbone, and examples thereof include known compounds which are known as epoxy curing agents. Among them, a compound represented by the formula (2) is preferred.

[In the formula (2), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms. R ¹² to R ¹⁴ are independently of each other and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or a fluorenyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group The hydrogen atom contained may also be substituted by a hydroxyl group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tertiary butyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a decyl group. , heptadecyl and undecyl.

As the cyanoalkyl group having 2 to 5 carbon atoms, for example, a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group, and a cyanopentyl group can be exemplified.

As the halogen atom, for example, a fluorine atom or a chlorine atom can be cited. And bromine atoms.

Examples of the fluorenyl group having 1 to 20 carbon atoms include a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group, an isovaleryl group, a trimethyl acetyl group, and a lauryl group. , nutmeg and stearin.

As the imidazole compound (J), for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl- 4-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4- Hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1 -benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1-(2 -cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl- 4-methylimidazole, 1-cyanomethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

In the case where the curable resin composition of the present invention contains the imidazole compound (J), the content thereof is preferably 100 parts by mass based on the total content of the resin (A) and the (meth)acrylic compound (B). 0.1 parts by mass or more and 25 parts by mass or less, preferably 0.2 parts by mass or more and 15 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (J) is within the above range, the obtained cured film tends to be excellent in transparency in the visible light region.

<Solvent (E)>

The solvent (E) is a dialkyl glycol dialkyl ether, and a solvent (E1) and a solvent (E2).

The dialkyl glycol dialkyl ether is a solvent comprising a compound represented by the formula (E').

[In the formula (E'), R ^e1 is an alkanediyl group having 1 to 3 carbon atoms.

R ^e2 and R ^e3 are independent of each other and represent an alkyl group having 1 to 4 carbon atoms. ]

Examples of the alkanediyl group of R ^e1 include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and the like, and an ethyl group or a propane-1 is used. 2-diyl is preferred.

^Examples of the alkyl group of 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. Desirably, methyl and ethyl are preferred.

Examples of the dialkyl glycol dialkyl ether include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol dipropyl ether. And diethylene glycol dialkyl ether such as diethylene glycol dibutyl ether; dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; and the like.

Among them, the dialkyl glycol dialkyl ether is preferably diethylene glycol dialkyl ether, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether are preferred, and diethylene glycol is used. Ethyl methyl ether is more preferred.

The solvent (E1) is different from the dialkyl glycol dialkyl ether, and the evaporation rate is a solvent 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 desirably 45 or more and less than 80, preferably 50 or more and less than 75.

In the present specification, the evaporation rate is a so-called evaporation rate of a solvent which is vaporized per unit area per unit time. The evaporation rate is expressed at a temperature of 23 ° C, relative The ratio of the evaporation rate of the sample (solvent) to the evaporation rate (100) of n-butyl acetate in 50% humidity. Specifically, the method of measuring is to set up a chemical scale and a 70 mm disk placed in No. 2 filter paper (70 mm ,) in a hood that may supply nitrogen gas, and one side is n-butyl acetate. On the other hand, the sample was placed in 1.0 g, and the inside of the extraction cabinet was supplied with nitrogen at a flow rate of 30 NL/ml. The weight of n-butyl acetate and the sample was measured simultaneously every 60 seconds, and 60 seconds passed. The average of the evaporation rates was calculated from the weight of 120 seconds and 180 seconds 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 (evaporation rate: 62), and propylene glycol monoethyl ether (evaporation rate: 46). ; an ester solvent such as methyl pyruvate (evaporation rate: 42), methyl propionate (evaporation rate: 45); a ketone solvent such as 2-butanone (evaporation rate: 40); aroma such as xylene (evaporation rate: 70) A hydrocarbon solvent; an alcohol solvent such as 1-butanol (evaporation rate: 47), 2-butanol (evaporation rate: 89), isobutanol (evaporation rate: 74), and the like.

Among them, 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 different from the dialkyl glycol dialkyl ether, and the evaporation rate is a solvent having 13 or more and less than 40 when the evaporation rate of butyl acetate is taken as 100. The evaporation rate of the solvent (E2) is desirably 25 or more and less than 40, more preferably 30 or more and less than 40.

As the solvent (E2), ethylene glycol monoethyl ether (evaporation rate: 32), ethylene glycol monopropyl ether (evaporation rate: 20), ethylene glycol monobutyl ether (steaming) Hair speed: 19), propylene glycol monopropyl ether (evaporation rate: 21) and other ether solvents; methyl lactate (evaporation rate: 29), ethyl lactate (evaporation rate: 22), ethyl pyruvate (evaporation rate: 31 Ester solvent; 3-methoxybutyl acetate (evaporation rate: 14), propylene glycol monomethyl ether acetate (evaporation rate: 33), propylene glycol monoethyl ether acetate (evaporation rate: 19), propylene glycol Monoethyl ether propionate (evaporation rate: 19), ethylene glycol monomethyl ether acetate (evaporation rate: 31), ethylene glycol monoethyl ether acetate (evaporation rate: 21), 3-methoxy Ether ester solvent such as methyl propyl propionate (evaporation rate: 32); 4-hydroxy-4-methyl-2-pentanone (evaporation rate: 15), diisobutyl ketone (evaporation rate: 20), cyclohexanone A ketone solvent such as (evaporation rate: 23); a guanamine solvent such as N,N-dimethylformamide (evaporation rate: 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 dialkyl glycol dialkyl ether, respectively, relative to the total amount of the solvent (E): 1 to 45 mass% solvent (E1): 5 to 80 mass% solvent (E2) 5 to 80% by mass, preferably dialkyl glycol dialkyl ether: 10 to 40% by mass of the solvent (E1): 10 to 70% by mass of the solvent (E2): more preferably 10 to 70% by mass.

The evaporation rate of the solvent (E) of the mixed solvent is preferably 55 or more and 90 or less, preferably 55 or more and 85 or less, more 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 at the time of drying under reduced pressure is short, and in particular, coating of the curable resin composition can provide high film flatness.

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

<Other ingredients>

In the curable resin composition of the present invention, if necessary, a filler, another polymer compound, a thermal radical generator, an ultraviolet absorber, a chain shifting agent, an adhesion promoter, etc. may be contained in the field. A conventional additive.

Examples of the filler include glass, cerium oxide, and aluminum oxide.

Examples of other polymer compounds include thermosetting resins such as maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Such as thermoplastic resin.

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

As the ultraviolet absorber, it can be mentioned that 2-(3-tert-butyl-2- Hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone and the like.

Examples of the chain shifting agent include decanethiol and 2,4-diphenyl-4-methyl-1-pentene.

Examples of the adhesion promoter include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, and 3-glycidoxy propyl trimethoxide. Baseline, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethyl Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methyl Acryloxypropyltrimethoxydecane, 3-sulfhydrylpropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-triisocyanatepropyltriethoxydecane, N-2- (Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, N-2- (Aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethyl Oxydecane, 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyl Triethoxy decane and the like.

The curable resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. In the curable resin composition of the present invention, the content of the colorant is usually less than 1% by mass, and preferably not more than 0.5% by mass, based on the entire composition.

Further, the curable resin composition of the present invention is filled in a quartz tube having an optical path length of 1 cm, and a transmittance at a wavelength of 400 to 700 nm is measured using a spectrophotometer, and the average transmittance is preferably 70% or more. More preferably, it is more than 80%.

In the curable resin composition of the present invention, when the cured film is used, the average transmittance of the cured film is desirably 90% or more, and more preferably 95% or more. This average transmittance is an average value of the case where the cured film having a thickness of 2 μm after heat hardening (100 ° C to 250 ° C, 5 minutes to 3 hours) is measured at a wavelength of 400 to 700 nm using a spectrophotometer. Thereby, it is possible to provide a cured film excellent in transparency in the visible light region.

<Method for Producing Curable Resin Composition>

The curable resin composition of the present invention is a resin (A), a solvent (E), and, if necessary, a (meth)acrylic compound (B), an epoxy resin (C), and a polymerization initiator ( D), a polymerization starting aid (D1), an antioxidant (F), a surfactant (H), a polyvalent carboxylic acid (G), an imidazole compound (J) and other ingredients, which are mixed by a conventional method. Can be manufactured. After mixing, it is preferably filtered by a filter having a pore diameter 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 to a substrate and hardening it by heat.

More specifically, the method for producing a cured film of the present invention comprises the following steps (1) to (3).

Step (1) A step of coating the curable resin composition of the present invention on a substrate.

Step (2) A step of drying the applied curable resin composition under reduced pressure to form a composition layer.

Step (3) a step of heating the composition layer.

Further, the curable resin composition of the present invention contains a polymerization initiator (D) In the case, a patterned cured film can be produced by performing the following steps.

Step (1) A step of coating the curable resin composition of the present invention on a substrate.

Step (2) A step of drying the applied curable resin composition under reduced pressure to form a composition layer.

Step (2a) is a step of exposing the composition layer through a photomask.

Step (2b) A step of developing the exposed composition layer.

Step (3) a step of heating the developed composition layer.

The step (1) is a step of applying the curable resin composition of the present invention onto a substrate.

Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and/or a driving circuit may be formed on the substrate.

The coating on the substrate is preferably carried out using a coating device such as a spin coater, a slit and a spin coater, a slit coater, an inkjet, a roll coater, or a dip coater.

The step (2) is a step of drying the applied curable resin composition under reduced pressure to form a composition layer. By performing this step, volatile components such as a solvent in the curable resin composition are removed.

The drying under reduced pressure is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa.

It can also be dried by heating (pre-baked) before or after drying under reduced pressure. The heat drying is usually carried out using a heating device such as an oven or a hot plate. The heating and drying temperature is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, as the heating and drying time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

Step (3) is a step of heating the composition layer (post-baking). The composition layer is hardened by heating to form a cured film. Heating is usually carried out 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 from 1 to 120 minutes, more preferably from 10 to 60 minutes.

The step (2a) is a step of exposing the composition layer formed by the step (2) through the photomask. The photomask is a removed portion corresponding to the composition layer, and a photomask that can form a light shielding portion is used. The formation of the light shielding portion is not particularly limited and can be selected depending on the intended use.

As the light source for exposure, a light source for generating light of a wavelength of 250 to 450 nm is preferred. For example, light of less than 350 nm may be cut by using a filter that cuts the wavelength region, or light of a vicinity of 436 nm, around 408 nm, and around 365 nm may be selected, and band pass filtering for taking out such wavelength regions may be used. Bandpass filter. Examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

Or it is suitable to uniformly align the light with the entire exposed surface to conform to the correct position of the mask and the composition layer, and it is preferable to use an exposure device such as a mask aligner or a stepper.

Step (2b) A step of developing the exposed composition layer. The exposed composition layer is brought into contact with the developer, and by development, the unexposed portion of the composition layer is dissolved in the developer to be removed, and a patterned composition layer is formed on the substrate.

The developer is an aqueous solution of a basic compound such as calcium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of the basic compound is desirably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. %. Further, a surfactant may also be contained.

For the development method, any one of puddle, dip, and spray may be used. Furthermore, the substrate can be tilted at any angle during development.

After development, it is preferably washed with water.

The step (3a) is a step of heating the developed composition layer. In the same manner as in the above step (3), the patterned composition layer is cured by heating, and a patterned cured film is formed on the substrate.

The hardened film thus obtained has a short time in the drying step, and is excellent in flatness, and can be used, for example, as a color filter substrate or a touch panel used in a liquid crystal display device, an organic EL display device, or an electronic paper. , protective film or cover film is used. As a result, it is possible to manufacture a display device having a high-quality cured film with high productivity.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The "%" and "parts" in the examples are mass% and mass parts unless otherwise specified.

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen atmosphere was set at a flow rate of 0.02 L/min of nitrogen gas, and 140 parts of diethylene glycol ethyl methyl ether was placed, and the mixture was heated to 70 ° C while stirring. Next, 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} 360 parts, dissolved in 190 parts of diethylene glycol ethyl methyl ether to prepare a solution, which was sprayed for 4 hours using a drip pump, and dropped into a flask kept at 70 ° C.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 240 parts of diethylene glycol ethyl methyl ether, and other drops were used. The pump was pumped for 5 hours and dripped into the flask. After the dropwise addition of the polymerization initiator solution was terminated, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a solid polymer (resin Aa) of 42.3%. The obtained resin Aa had a weight average molecular weight (Mw) of 8,000, a molecular weight distribution (Mw/Mn) of 1.91, and an acid value in terms of a solid content of 60 mg-KOH/g. The resin Aa has the following structural unit.

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

Device: K2479 (made 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 materials for calibration: TSK Standard Polystyrene F-40, F-4, F-288, A-2500, A-500 (TOSOH (share) system)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight of the above-mentioned converted polystyrene was taken as a molecular weight distribution.

Examples 1 to 5 and Comparative Example 1 <Modulation of Curable Resin Composition>

Each component shown in Table 1 was mixed at the ratio shown in Table 1, and the curable resin composition was obtained.

Further, in Table 1, the content of the resin (A) is expressed by parts by mass in terms of solid content.

Resin (A); Aa; Resin Aa

(meth)acrylic compound (B); dipentaerythritol hexaacrylate (KAYARD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Epoxy resin (C); bisphenol A type epoxy resin (JER157S70; Mitsubishi Chemical (share) system)

Polymerization initiator (D); Da; N-benzofluorenyl-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; BASF Corporation System; O-mercaptopurine compound)

Polymerization initiator (D); Db; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; Baotu Valley Chemical Co., Ltd.; biimidazole compound)

Polymerization initiator (D1); 2-[2-oxy-2-(naphthyl)ethylidene]-3-methylbenzothiazoline (compound represented below)

Thiol compound (T): pentaerythritol phthalate (PEMP; SC organic chemistry)

Antioxidant (F); 1,3,5-gin (4-hydroxy-3,5-di-tertiary-butylbenzyl)-1,3,5-triazine-2,4,6-(1H , 3H, 5H)-trione (IRGANOX (registered trademark) 3114; manufactured by BASF Corporation)

Polyvalent carboxylic acid (G); butane tetracarboxylic acid (Rikacid BT-W; New Japan Physical and Chemical Corporation)

Imidazole compound (J); 1-benzyl-2-phenylimidazole (Curezol 1B2PZ; Shikoku Chemical Industry Co., Ltd.)

Surfactant (H); polyether modified oyster sauce (Toray silicon SH8400; Toray Dowcorning (manufactured by the company)

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 a solid component of the curable resin composition which is intended to be mixed as "solid component %" of Table 1, and the solvent components (Ea) to (Eb) in the solvent (E) represent the solvent (E). The quality ratio is %.

<Measurement of evaporation rate of solvent>

In a hood that may supply nitrogen gas, set up a chemical scale and two 70mm trays of No. 2 filter paper (70mm ψ), one side is n-butyl acetate, the other side is a sample, and each is placed in 1.0g. In the extraction cabinet, nitrogen gas is supplied at a flow rate of 30 NL/ml. The weight of n-butyl acetate and the sample is measured simultaneously every 60 seconds, and will be 60 seconds, 120 seconds, and 180 seconds. The evaporation rate was calculated from the weight. The average value was taken as the evaporation rate of the sample.

The solvent (E) contained in the curable resin composition of the examples and the comparative examples was measured as a sample, and the evaporation rate at the time when the evaporation rate of butyl acetate was taken as 100 was shown in Table 2.

<Viscometry>

The viscosity of the obtained curable resin composition was measured using a viscometer (model: TV-30: manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 4.

<Measurement of transmittance of composition>

For the obtained curable resin composition, an ultraviolet visible light near-infrared luminometer (V-650; manufactured by JASCO Corporation) (quartz tube, optical path length; 1 cm) was used to measure the average transmittance in 400 to 700 nm ( %). The results are shown in Table 4.

<Production of cured film>

A 2" square glass substrate (Eagle XG, manufactured by Corning) was washed with a neutral detergent, water, and isopropyl alcohol, and dried, and the thickness of the curable resin composition was baked on the glass substrate. An attempt was made to spin coat in a 2.0 μm manner, followed by pre-baking at 90 ° C for 10 minutes in a clean oven. Thereafter, it was post-baked at 230 ° C for 40 minutes to obtain a cured film.

<Measurement of film thickness>

The film thickness of the cured film was measured using a contact film thickness measuring device (DEKTAK 6M; manufactured by Arpak Co., Ltd.) to measure a width of 500 μm at a measurement speed of 10 seconds.

<Measurement of Transmittance of Hardened Film>

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

<Evaluation of Decompression Drying Time>

A 15 cm square ITO film-forming glass substrate was used, and the curable resin composition was subjected to a slit mold coater (Takudai-100, manufactured by Itoji Co., Ltd.), and the film thickness after baking was attempted to be 1.5 μm. Coating. After that, the number of revolutions of the drum pump in a vacuum dryer (VCD Macrotec Co., Ltd.) was 1000 rpm. The number of revolutions of the booster pump was 700 rpm, and the time until the pressure reduction of 66 Pa was reached under the condition of a normal temperature of 25 ° C. When the vacuum drying time was short, the productivity of the cured film was high, and the results are shown in Table 4.

<Slot Nozzle Dryness Evaluation>

A 15 cm square ITO film-forming glass substrate was coated with a curable resin by using a slit mold coater (Takudai-100, manufactured by Itochu Co., Ltd.) under the condition that the film thickness after baking was 1.5 μm. Things.

Thereafter, the nozzle of the slit die coater was directly placed for 1 minute, and then the curable resin composition was applied onto a 15 cm square ITO film-forming glass substrate in the same manner as described above without washing the nozzle tip.

The substrate of the curable resin composition was applied to the tip of the nozzle, and the pressure reduction dryer (VCD Macrotec Co., Ltd.) was used to reduce the pressure to 0.5 torr, and then dried under reduced pressure, and then on a hot plate. The composition layer was formed by prebaking at 90 ° C for 2 minutes.

After cooling, the surface of the composition layer was irradiated with a Na lamp to visually observe the composition level. Only the case where the vertical line streak is confirmed is regarded as X, and the case where it can be confirmed is regarded as Δ, and the case where it cannot be confirmed is regarded as ○, and the result is shown in Table 4.

<Flatness evaluation; production of evaluation substrate>

The components shown in Table 3 were mixed at a ratio shown in Table 3 to obtain a colored photosensitive resin composition.

A 15 cm square ITO-formed glass substrate was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and then dried. On the substrate, the photosensitive resin composition was colored, and the film thickness after the baking was attempted to be 1.6 μm. The way is to spin coating. Next, in an economical oven, prebaking at 90 ° C for 3 minutes to form a colored composition layer. After cooling, the distance between the colored composition layer on the substrate and the quartz glass mask was set to 100 μm, and an exposure machine (TME-150RSK; Topcon (light source; ultrahigh pressure mercury lamp) was used in an atmosphere, Light was irradiated with an exposure amount of 100 mJ/cm ² (based on 365 nm). Further, this light was irradiated with light from an ultrahigh pressure mercury lamp to pass through an optical filter (UV-35; manufactured by Asahi tecnoglass Co., Ltd.). Further, as a mask, a mask for forming a line and space pattern having a line width of 30 μm was used. The colored composition layer after the light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide in a water-based developing solution at 23 ° C for 80 seconds, and washed with water, and then, in an oven, at 220 ° C. After the minute baking, a colored pattern of lines and spaces having a line width of 30 μm was formed, and a substrate for evaluation was prepared.

<Flatness Evaluation 1>

In the substrate for the evaluation, a slit coater (Takudai-100, manufactured by Itoji Co., Ltd.) was used, and the film thickness after baking was applied to a condition of 1.5 μm to apply a curable resin composition. Then, the pressure reduction dryer (VCD Macrotec Co., Ltd.) was vacuum-dried at a reduced pressure of 0.5 torr, pre-baked at 90 ° C for 2 minutes on a hot plate, and allowed to cool, at 230 ° C. After baking for 40 minutes, a cured film was formed.

In the cured film of the evaluation substrate, the film thickness of the portion where the colored pattern was not formed under the cured film was measured, and it was confirmed to be 1.5 μm.

The undulation difference of the surface of the cured film formed on the colored pattern is measured. When the height difference is 0.5 μm or less, the flatness of the cured film is excellent, and it is particularly suitable as a protective film for a color filter. The results are shown in Table 4.

<Flatness Evaluation 2>

In the substrate for the evaluation, a slit coater (Takudai-100, manufactured by Itoji Co., Ltd.) was used, and the film thickness after baking was applied to a condition of 1.5 μm to apply a curable resin composition. After that, the pressure reduction dryer (manufactured by VCD Macrotec Co., Ltd.) was dried under reduced pressure until it became 0.5 torr, and prebaked on a hot plate at 90 ° C for 2 minutes. After cooling, the exposure machine was used. TME-150RSK; Topcon (source), light source; ultra-high pressure mercury lamp), irradiated with light at an exposure of 250 mJ/cm ² (based on 365 nm) in an atmospheric environment. Further, the light is irradiated from the ultrahigh pressure mercury lamp to pass through an optical filter (UV-35; manufactured by Asahi tecnoglass). The composition layer after the light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 60 seconds, and after washing with water, at 230 ° C for 20 minutes. Bake to form a cured film.

In the cured film on the evaluation substrate, the film thickness of the colored pattern portion under the cured film was measured, and it was confirmed to be 1.5 μm.

The undulation difference of the surface of the cured film formed on the colored pattern is measured. When the height difference is 0.5 μm or less, the flatness of the cured film is excellent, and it is particularly suitable as a protective film for a color filter. The results are shown in Table 4.

<Resolution Evaluation>

As a substrate, a 2 Å square glass substrate (Eagle XG, manufactured by Corning Co., Ltd.) was used, except that the light was irradiated with an exposure amount of 100 mJ/cm ² (based on 365 nm) through a photomask. A patterned cured film was produced in the same manner as in the flatness evaluation 2. Further, as a photomask, a photomask which forms a line pattern of 20 μm is used.

The obtained cured film was observed by a scanning electron microscope (S-4000; manufactured by Hitachi High-Technology Co., Ltd.), and was regarded as ○ when the solution was 20 μm in line and space, and as X when there was no image. The results are shown in Table 4.

From the results of Table 4, it was confirmed that the curable resin composition of the present invention has a short drying time under reduced pressure, and the flatness of the cured film is also excellent. Therefore, the curable resin composition of the present invention can produce a cured film having high productivity and high performance.

According to the present invention, it is possible to provide a curable resin composition which has a short drying time when the curable resin composition is applied onto a substrate and then dried under reduced pressure. 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 (6)

A curable resin composition comprising a curable resin and a solvent, wherein the solvent contains a dialkyl glycol dialkyl ether, and a solvent (E1), a solvent (E2), a dialkyl glycol dialkyl ether The content is 1% by mass or more and 45% by mass or less based on the total amount of the solvent, and the solvent (E1) is different from the dialkyl glycol dialkyl ether, and the evaporation rate is regarded as the evaporation rate of butyl acetate. At 100 hours, it is an ether solvent of 40 or more and 100 or less. The solvent (E2) is different from the dialkyl glycol dialkyl ether, and the evaporation rate is 13 or more when the evaporation rate of butyl acetate is taken as 100. Up to 40 ether ester solvent. The curable resin composition according to claim 1, wherein the curable resin is a structural unit containing at least one selected from the group consisting of a source of a free unsaturated carboxylic acid and an unsaturated carboxylic anhydride. A copolymer with a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The curable resin composition according to claim 1 or 2, which further comprises an antioxidant. A cured film formed of the curable resin composition according to any one of claims 1 to 3. A display device comprising the cured film of claim 4 of the patent application. A method for producing a cured film, comprising: (1) a step of applying a curable resin composition according to any one of claims 1 to 3 to a substrate, and (2) applying the curable resin The composition is dried under reduced pressure to form a composition layer Step, (3) a step of heating the composition layer.