JP7061843B2 - Curable resin composition and cured film - Google Patents

Description

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

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

Japanese Unexamined Patent Publication No. 2010-152335

The curable resin composition usually forms a cured film by applying it to a substrate and heating it. Here, when the surface to be coated has irregularities, it is difficult to obtain a cured film having a high surface flatness. For example, when a cured film is formed by applying a curable resin composition to a substrate on which a colored pattern is formed and heating the substrate, and this is used as an overcoat, an overcoat having a high surface flatness can be obtained. Was difficult.

For example, it is expected that the flatness of the surface can be improved by thickening the overcoat, but considering other characteristics of the object on which the overcoat is formed, the thickness of the overcoat is as an overcoat. There is an aspect that the thinner it is, the more preferable it is in the range in which the function of is expressed.

An object of the present invention is to provide a curable resin composition capable of forming a cured film having a high surface flatness, and a cured film formed from the curable resin composition.

The present invention includes the following inventions.
[1] Contains a curable resin and a solvent,
The solvent contains 20% by mass or more of the first solvent and contains 20% by mass or more.
A curable resin composition having a boiling point of the first solvent of 200 ° C. or higher.

[2] The curable resin composition according to [1], wherein the solvent contains 20% by mass or more and 80% by mass or less of the first solvent.

[3] The curable resin composition according to [1] or [2], wherein the first solvent has a boiling point of 220 ° C. or higher.

[4] The first solvent is at least one selected from the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane and triethylene glycol monobutyl ether. The curable resin composition according to any one of [1] to [3], which is a seed.

[5] The curable resin composition according to any one of [1] to [4], wherein the solvent further contains a second solvent and the boiling point of the second solvent is less than 200 ° C.

[6] The second solvent is at least one selected from the group consisting of a solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C. and a solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. [5]. Curable resin composition.

[7] The second solvent contains the solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C.
The solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C. is selected from the group consisting of methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and ethylene glycol monomethyl ether acetate. The curable resin composition according to [6], which is at least one kind.

[8] The second solvent contains the solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C.
The solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. is at least one selected from the group consisting of diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, and 3-methoxybutyl acetate. The curable resin composition according to [6] or [7].

[9] The curable resin has a structural unit derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and cyclic ethers having 2 to 4 carbon atoms. The curable resin composition according to any one of [1] to [8], which comprises a copolymer containing a structural unit derived from a monomer having a structure and an ethylenically unsaturated bond.

[10] The curable resin composition according to any one of [1] to [9], which comprises at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin, in addition to the curable resin. thing.

[11] The curable resin composition according to any one of [1] to [10], further comprising an antioxidant.

[12] A curable resin composition containing a curable resin and a solvent.
A sample obtained by applying the curable resin composition on a substrate so that the film thickness after heat treatment is 1.8 μm is dried in a vacuum dryer under the condition of a temperature of 25 ° C. until the pressure reduction reaches 66 Pa. When the vacuum drying treatment for heating, the heat drying treatment for heating at a temperature of 100 ° C. for 3 minutes, and the heat treatment for heating at a temperature of 230 ° C. for 30 minutes are performed in sequence, the sample immediately after the application of the curable resin composition is performed. Assuming that the mass is 100, the mass of the sample after the vacuum drying treatment and before the heat drying treatment is 30 or more, and the mass of the sample after the heat treatment is 20 or less, [1] to [12]. The curable resin composition according to any one.

[13] A cured film formed from the curable resin composition according to any one of [1] to [12].

[14] The cured film according to [13], which is a protective film for a color filter or a touch panel.
[15] A display device including the cured film according to [14].

[16] A method for producing a cured film, which comprises a step of applying the curable resin composition according to any one of [1] to [12] onto a substrate, and a step of heating the curable resin composition after coating. ..

According to the present invention, it is possible to provide a curable resin composition capable of forming a cured film having a high surface flatness.

It is a figure which shows the profile of the surface shape (the surface shape of a coloring pattern, the surface shape of a cured film) of the evaluation sample of Example 1. FIG. It is a figure which shows the profile of the surface (the surface shape of a coloring pattern, the surface shape of a cured film) of the evaluation sample of the comparative example 1. FIG.

In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of kinds unless otherwise specified.

The curable resin composition of the present invention contains a curable resin (hereinafter sometimes referred to as "resin (A)") and a solvent (E), and the solvent (E) is the solvent (E1) ("first". Also referred to as "solvent") in an amount of 20% by mass or more. The boiling point of the solvent (E1) is 200 ° C. or higher. The solvent (E) may contain a solvent (E2) (also referred to as “second solvent”) having a boiling point different from that of the solvent (E1). The boiling point of the solvent (E2) is less than 200 ° C.

Further, the curable resin composition of the present invention preferably contains at least one component selected from the group consisting of the reactive monomer (B), the antioxidant (F), and the surfactant (H). As the reactive monomer (B), a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter, may be referred to as “(meth) acryloyl group”) (hereinafter, “(meth)”. It may be referred to as "acrylic compound (B1)"), a compound (B2) represented by the formula (1), and the like.

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

[In formulas (a) and (b), R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other. ]
Further, the curable resin composition of the present invention is at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter, may be referred to as "epoxy resin (C)"), and polymerization initiation. At least one compound selected from the group consisting of the agent (D), the polymerization initiation aid (D1), the thiol compound (T), the polyvalent carboxylic acid anhydride and the polyvalent carboxylic acid (hereinafter, "polyvalent carboxylic acid (G)". ) ”), And may contain at least one component selected from the group consisting of the imidazole compound (J).

<Resin (A)>
The resin (A) is a curable resin, preferably a thermosetting resin, more preferably a resin that cures with heat of 60 ° C. or higher, and an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It has a structural unit derived from at least one monomer selected from the group consisting of substances (hereinafter sometimes referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. It is more preferable that the copolymer contains a structural unit derived from a monomer (hereinafter sometimes referred to as “(b)”). The copolymer is further derived from a monomer (hereinafter, may be referred to as "(c)") that is copolymerizable with (a) and does not have a cyclic ether structure having 2 to 4 carbon atoms. It may have a structural unit. The epoxy resin (C) described later is a resin having curability, but the resin (A) does not contain this.

The resin (A) is preferably the following resin [K1] and resin [K2].
Resin [K1]: Copolymer of (a) and (b);
Resin [K2]: A copolymer of (a), (b) and (c).

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Bicyclounsaturated compounds containing a carboxy group such as hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-enehydride; Anhydride mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as [meth) acryloyloxyethyl] and mono-phthalate [2- (meth) acryloyloxyethyl];
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Of these, (a) is preferably (meth) acrylic acid, maleic anhydride, or the like, and more preferably (meth) acrylic acid, in terms of copolymerizability and solubility in an alkaline aqueous solution. In addition, in this specification, "(meth) acryloyl" represents at least one kind selected from the group consisting of acryloyl and methacryloyl. Notations such as "(meth) acrylic acid" and "(meth) acrylate" have the same meaning.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. say. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.

Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single having an oxetanyl group and an ethylenically unsaturated bond. Examples include a metric (b2) (hereinafter sometimes referred to as "(b2)") and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"). Be done.

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

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene , 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

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

[In the formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You may. X ^b1 and X ^b2 represent a single bond, -R b3-, * -R ^b3 -O-, * -R ^b3 -S- or * -R ^b3 - ^NH- . R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O. ]
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like. The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

Examples of R ^b1 and R ^b2 include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.

Examples of X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O-, and * -CH ₂ CH ₂ -O-, and more preferably a single bond, * -CH ₂ . CH ₂ -O- can be mentioned. * Represents a bond with O.

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

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15), preferably formulas (II-1) and (II). -3), the compound represented by the formula (II-5), the formula (II-7), the formula (II-9) or the formula (II-11) to the formula (II-15) can be mentioned, and more preferably. Examples thereof include compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in admixture at any ratio. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to the molar basis. It is 90:10, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

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

As (b), (b1) is preferable in that the reliability of the obtained cured film such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the curable resin composition has excellent storage stability.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and in the case of "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) Oxycarbonyl) Bicyclo unsaturated compounds such as bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like can be mentioned.

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

In the resin [K1], the ratio of the structural units derived from each monomer is the ratio of the structural units constituting the resin [K1] to all the structural units.
Structural unit derived from (a); 5-60 mol%,
Structural unit derived from (b); preferably 40 to 95 mol%.
Structural unit derived from (a); 10-50 mol%,
The structural unit derived from (b); more preferably 50 to 90 mol%.

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

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (published by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st print, published on March 1, 1972). It can be manufactured with reference to the cited documents described in the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any solvent as long as it dissolves each monomer, and examples thereof include the solvents described below used in the curable resin composition.

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

In the resin [K2], the ratio of the structural units derived from each is the ratio of all the structural units constituting the resin [K2].
Structural unit derived from (a); 2-40 mol%,
Structural unit derived from (b); 2-95 mol%,
Structural unit derived from (c); preferably 1 to 65 mol%.
Structural unit derived from (a); 5 to 35 mol%,
Structural unit derived from (b); 5-80 mol%,
The structural unit derived from (c); more preferably 1 to 60 mol%.

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

As a specific example of the resin [K1], a compound represented by (meth) acrylic acid / formula (I-1) (hereinafter, the compound may be abbreviated as “formula (I-1)”. Similarly, compounds represented by other formulas such as compounds represented by -2) are also represented by abbreviations (formula only), and (meth) acrylic acid / formula (I-2). Polymers, (meth) acrylic acid / copolymer of formula (I-3), (meth) acrylic acid / copolymer of formula (I-4), (meth) acrylic acid / formula (I-5) Copolymer, (meth) acrylic acid / copolymer of formula (I-6), (meth) acrylic acid / copolymer of formula (I-7), (meth) acrylic acid / formula (I-8) (Meta) acrylic acid / formula (I-9) copolymer, (meth) acrylic acid / formula (I-10) copolymer, (meth) acrylic acid / formula (I-11). ), (Meta) acrylic acid / formula (I-12) copolymer, (meth) acrylic acid / formula (I-13) copolymer, (meth) acrylic acid / formula (I-). 14) copolymer, (meth) acrylic acid / formula (I-15) copolymer, (meth) acrylic acid / formula (II-1) copolymer, (meth) acrylic acid / formula (II). -2) Copolymer, (meth) acrylic acid / formula (II-3) copolymer, (meth) acrylic acid / formula (II-4) copolymer, (meth) acrylic acid / formula ( II-5) copolymer, (meth) acrylic acid / formula (II-6) copolymer, (meth) acrylic acid / formula (II-7) copolymer, (meth) acrylic acid / formula (II-8) copolymer, (meth) acrylic acid / formula (II-9) copolymer, (meth) acrylic acid / formula (II-10) copolymer, (meth) acrylic acid / Polymer of formula (II-11), (meth) acrylic acid / copolymer of formula (II-12), (meth) acrylic acid / copolymer of formula (II-13), (meth) acrylic acid / Compound of formula (II-14), (meth) acrylic acid / copolymer of formula (II-15), (meth) acrylic acid / co-formula (I-1) / formula (II-1) Polymer, (meth) acrylic acid / formula (I-2) / formula (II-2) copolymer, (meth) acrylic acid / formula (I-3) / formula (II-3) copolymer , (Meta) acrylic acid / formula (I-4) / copolymer of formula (II-4), (meth) acrylic acid / formula (I-5) / copolymer of formula (II-5), ( Meta) Acrylic acid / Formula (I-6) / Formula (II-6) copolymer, (Meta) Acrylic acid / Formula (I-7) / Formula (II-7) copolymer, (Meta) Acrylic acid / Polymer of formula (I-8) / formula (II-8), (meth) acrylic acid / copolymer of formula (I-9) / formula (II-9), (meth) acrylic acid / formula (I-10) / Polymer of formula (II-10), (meth) acrylic acid / copolymer of formula (I-11) / formula (II-11), (meth) acrylic acid / formula (I) -12) / Polymer of formula (II-12), (meth) acrylic acid / copolymer of formula (I-13) / formula (II-13), (meth) acrylic acid / formula (I14) / Polymer of formula (II-14), (meth) acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth) acrylic acid / formula (I-1) / formula ( I-7) copolymer, (meth) acrylic acid / formula (I-1) / formula (II-7) copolymer, crotonic acid / formula (I-1) copolymer, crotonic acid / Polymer of formula (I-2), crotonic acid / copolymer of formula (I-3), crotonic acid / copolymer of formula (I-4), crotonic acid / copolymer of formula (I-5) Polymer, polymer of crotonic acid / formula (I-6), copolymer of crotonic acid / formula (I-7), copolymer of crotonic acid / formula (I-8), crotonic acid / formula ( I-9) copolymer, crotonic acid / formula (I-10) copolymer, crotonic acid / formula (I-11) copolymer, crotonic acid / formula (I-12) copolymer , Crotonic acid / polymer of formula (I-13), crotonic acid / copolymer of formula (I-14), crotonic acid / copolymer of formula (I-15), crotonic acid / formula (II-). 1) Polymer, Crotonic Acid / Formula (II-2) Polymer, Crotonic Acid / Formula (II-3) Polymer, Crotonic Acid / Formula (II-4) Polymer, Croton Acid / formula (II-5) copolymer, crotonic acid / formula (II-6) copolymer, crotonic acid / formula (II-7) copolymer, crotonic acid / formula (II-8) Polymer, crotonic acid / copolymer of formula (II-9), crotonic acid / copolymer of formula (II-10), crotonic acid / copolymer of formula (II-11), crotonic acid / Polymer of formula (II-12), crotonic acid / copolymer of formula (II-13), crotonic acid / copolymer of formula (II-14), crotonic acid / copolymer of formula (II-15) Polymer, polymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2), copolymer of maleic acid / formula (I-3), maleic acid / formula ( I-4) copolymer, maleic acid / formula (I-5) copolymer, maleic acid / formula (I-6) copolymer, maleic acid / formula (I-7) copolymer , Polymeric acid / Polymer of formula (I-8), polymer of maleic acid / formula (I-9), copolymer of maleic acid / copolymer of formula (I-10), co-polymer of maleic acid / formula (I-11) Polymer, polymer of maleic acid / formula (I-12), copolymer of maleic acid / formula (I-13), copolymer of maleic acid / formula (I-14), maleic acid / formula ( I-15) copolymer, maleic acid / formula (II-1) copolymer, maleic acid / formula (II-2) copolymer, maleic acid / formula (II-3) copolymer , Maleic acid / polymer of formula (II-4), maleic acid / copolymer of formula (II-5), maleic acid / copolymer of formula (II-6), maleic acid / formula (II-) 7) Polymer, maleic acid / formula (II-8) copolymer, maleic acid / formula (II-9) copolymer, maleic acid / formula (II-10) copolymer, malein Acid / formula (II-11) copolymer, maleic acid / formula (II-12) copolymer, maleic acid / formula (II-13) copolymer, maleic acid / formula (II-14) Polymeric acid / copolymer of formula (II-15), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-1), (meth) acrylic acid / maleic acid anhydride Product / Polymer of formula (I-2), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-3), (meth) acrylic acid / maleic acid anhydride / formula (I-) 4) Polymer, (meth) acrylic acid / maleic acid anhydride / polymer of formula (I-5), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-6) , (Meta) acrylic acid / maleic acid anhydride / polymer of formula (I-7), (meth) acrylic acid / maleic acid anhydride / polymer of formula (I-8), (meth) acrylic acid / Maleic acid anhydride / Polymer of formula (I-9), (meth) acrylic acid / Maleic acid anhydride / Polymer of formula (I-10), (meth) acrylic acid / Maleic acid anhydride / Polymer of formula (I-11), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic acid anhydride / formula (I-13) Polymer, (meth) acrylic acid / maleic acid anhydride / polymer of formula (I-14), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (I-15), ( Meta) Acrylic acid / Maleic acid anhydride / Polymer of formula (II-1), (Meta) acrylic acid / Maleic acid anhydride / Polymer of formula (II-2), (Meta) acrylic acid / Malein Acid anhydride / copolymerization of formula (II-3) Body, (meth) acrylic acid / maleic acid anhydride / polymer of formula (II-4), (meth) acrylic acid / maleic acid anhydride / polymer of formula (II-5), (meth) acrylic Acid / maleic acid anhydride / polymer of formula (II-6), (meth) acrylic acid / maleic acid anhydride / polymer of formula (II-7), (meth) acrylic acid / maleic acid anhydride / Polymer of formula (II-8), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-9), (meth) acrylic acid / maleic acid anhydride / formula (II-10) ), (Meta) acrylic acid / maleic acid anhydride / polymer of formula (II-11), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-12), (Meta) acrylic acid / maleic acid anhydride / polymer of formula (II-13), (meth) acrylic acid / maleic acid anhydride / copolymer of formula (II-14), (meth) acrylic acid / Maleic acid anhydride / a copolymer of the formula (II-15) and the like can be mentioned.

Specific examples of the resin [K2] include (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-2) / methyl (meth). Polymer of acrylate, copolymer of (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate Combined, (meth) acrylic acid / formula (I-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate copolymer, (meth) ) Acrylic acid / formula (I-7) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / Polymer of formula (I-9) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-) 11) / Polymer of methyl (meth) acrylate, (meth) acrylic acid / formula (I-12) / polymer of methyl (meth) acrylate, (meth) acrylic acid / formula (I-13) / methyl Polymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate Polymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate copolymer , (Meta) acrylic acid / formula (II-3) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-4) / methyl (meth) acrylate copolymer, (meth) Acrylic acid / formula (II-5) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-7) / Methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-9) ) / Methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-11) / methyl ( Polymer of (meth) acrylate, (meth) acrylic acid / formula (II-12) / methyl (meth) acryle Polymers of (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate. Polymer, polymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, common weight of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Combined, (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclo Polymeric acid / formula (I-1) / dicyclopentanyl (meth) acrylate copolymer, maleic acid / formula (I-1) / dicyclopentanyl (meth) ) Polymer of acrylate, (meth) acrylic acid / maleic anhydride / formula (I-1) / polymer of dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / Methyl (meth) acrylate / dicyclopentanyl (meth) acrylate copolymer, crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate copolymer, maleic acid / formula (II-) 1) / Polymer of dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / polymer of dicyclopentanyl (meth) acrylate, (meth) Polymer of acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate, co-weight of (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate Combined, (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate Polymeric acid / formula (I-1) / phenyl (meth) acrylate copolymer, maleic acid / formula (I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid. / Maleic acid anhydride / formula (I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer Combined, crotonic acid / formula (II-1) / phenyl (meth) acrylate copolymer, maleic acid / formula (II-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid Polymer / formula (I) I-1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / Formula (I-1) / diethyl maleate copolymer, (meth) acrylic acid / formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate copolymer, crotonic acid / formula (I-1) / diethyl maleate copolymer, maleic acid / formula (I-1) / diethyl maleate copolymer, Copolymer of (meth) acrylic acid / maleic acid anhydride / formula (I-1) / diethyl maleate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate Polymer, crotonic acid / formula (II-1) / diethyl maleate copolymer, maleic acid / formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / maleic acid anhydride / Formula (II-1) / diethyl maleate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / diethyl maleate copolymer, (meth) acrylic acid / formula ( I-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / A copolymer of formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, a copolymer of crotonic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, Maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / 2-hydroxyethyl (meth) acrylate Copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, crotonic acid / formula (II-1) / 2-hydroxyethyl (Meta) acrylate copolymer, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / 2-Hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid /formula( I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Polymer, (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hepto-2-ene copolymer, crotonic acid / formula (I-1) ) / Bicyclo [2.2.1] hept-2-ene copolymer, maleic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) ) Acrylic acid / maleic acid anhydride / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / formula (I-1) / methyl (meth) ) Alico / bicyclo [2.2.1] hept-2-ene copolymer, crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene copolymer, malein Acid / formula (II-1) / bicyclo [2.2.1] hepto-2-ene copolymer, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / bicyclo [2.2] .1] Polymer of hept-2-ene, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / bicyclo [2.2.1] copolymer of hept-2-ene, (Meta) acrylic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / formula (II-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / Formula (I-1) / formula (II-1) / N-cyclohexylmaleimide copolymer, crotonic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, maleic acid / formula (I-1) ) / N-Cyclohexyl maleimide copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / N-cyclohexyl maleimide copolymer, (meth) acrylic acid / formula (I-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide copolymer, Crotonic acid / Formula (II-1) / N-cyclohexylmaleimide copolymer, Maleic acid / Formula (II-1) / N-cyclohexylmaleimide Polymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexyl maleimide copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / Polymer of N-cyclohexylmaleimide, polymer of (meth) acrylic acid / formula (I-1) / styrene, copolymer of (meth) acrylic acid / formula (II-1) / styrene, (me. T) Acrylic acid / formula (I-1) / formula (II-1) / styrene copolymer, crotonic acid / formula (I-1) / styrene copolymer, maleic acid / formula (I-1) / Polymer copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / polymer of styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Polymers of styrene, crotonic acid / formula (II-1) / copolymers of styrene, maleic acid / formula (II-1) / copolymers of styrene, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / Polymer copolymer, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / formula (I-1) / N-Cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula (II-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula (I-1) / formula ( II-1) / N-cyclohexyl maleimide / styrene copolymer, crotonic acid / formula (I-1) / N-cyclohexyl maleimide / styrene copolymer, maleic acid / formula (I-1) / N-cyclohexyl Maleimide / styrene copolymer, (meth) acrylic acid / maleic acid anhydride / formula (I-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula (I-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer, crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene copolymer, maleic acid / formula (II-1) / N- Polymer of cyclohexyl maleimide / styrene, (meth) acrylic acid / maleic acid anhydride / formula (II-1) / polymer of N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / Methyl (meth) acrylate / N-cyclohexylmaleimide / styrene copolymer and the like can be mentioned.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20, It is 000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight (Mw) 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 preferably 1.1 to 6.0, more preferably 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, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, and further preferably 50 mg-KOH / g. It is 135 mg-KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titrating with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the substrate.

The content of the resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 40% by mass, based on the solid content of the curable resin composition of the present invention. It is 70% by mass. When the content of the resin (A) is within the above range, the obtained cured film tends to have excellent heat resistance, adhesion to the substrate, and chemical resistance. Here, the solid content of the curable resin composition means an amount obtained by subtracting the content of the solvent (E) from the total amount of the curable resin composition of the present invention.

The curable resin composition of the present invention is further selected as the resin (A) from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter, the resin is referred to as "epoxy resin (C)). ".) May be included.

<Reactive monomer (B)>
As the reactive monomer (B), a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group (hereinafter, may be referred to as “(meth) acryloyl group”) (hereinafter, the compound is referred to as “ (Meth) acrylic compound (B1) ”), a compound (B2) represented by the formula (1) described later, and the like are included.

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

Examples of the (meth) acrylic compound (B1) having one (meth) acryloyl group include the same compounds as those mentioned in the above (a), (b) and (c), and preferably (meth) acrylic acid. Examples include esters.

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

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanuratetri (meth) acrylate, and the like. Trimethylol ethoxylated propanetri (meth) acrylate, propoxylated trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripenta Ellisritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate And acid anhydride reaction product, dipentaerythritol penta (meth) acrylate and acid anhydride reaction product, tripentaerythritol hepta (meth) acrylate and acid anhydride reaction product, caprolactone-modified trimethyl propanetri ( Meta) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripenta Elythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction with caprolactone-modified tripentaerythritol hepta (meth) acrylate and acid anhydride Things etc. can be mentioned.

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

When the curable resin composition of the present invention contains the (meth) acrylic compound (B1), the content thereof is preferably 20 to 100 parts by mass, more preferably 20 parts by mass with respect to 100 parts by mass of the content of the resin (A). Is 25 to 70 parts by mass. When the content of the (meth) acrylic compound is within the above range, the chemical resistance and mechanical strength of the obtained cured film can be improved.

The compound (B2), which is a suitable example of the reactive monomer (B), is represented by the formula (1).

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

[In formulas (a) and (b), R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other. ]
Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an octyl group and the like. As ^R4 , a hydrogen atom or a methyl group is preferable, and a hydrogen atom is more preferable. As ^R5 , a hydrogen atom or a methyl group is preferable.

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

Examples of the compound (B2) include compounds represented by formulas (1-1) to (1-7), and preferably compounds represented by formulas (1-1) to (1-4). Compounds are mentioned.

When the curable resin composition of the present invention contains the compound (B2), the content thereof is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the content of the resin (A). It is a mass part. When the content of the compound (B2) is within the above range, the heat resistance of the obtained cured film can be improved.

<Epoxy resin (C)>
The epoxy resin (C) is at least one compound from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin.

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

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

The epoxy resin (C) used in the curable resin composition of the present invention is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, an o-cresol novolac type epoxy resin, or a polyphenol type epoxy resin. Examples thereof include glycidyl ether type epoxy resins such as, and more preferably bisphenol A type epoxy resins.

The glycidyl ether type epoxy resin as described above can be synthesized by condensing the corresponding phenol compound and epichlorohydrin in the presence of a strong alkali using a conventionally known method. Such a reaction can be carried out by a method conventionally known to those skilled in the art.
Further, a commercially available product may be used. Examples of commercially available bisphenol A type epoxy resins include jER157S70, Epicoat 1001, Epicoat 1002, Epicoat 1003, Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010, and Epicoat 828 (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available bisphenol F type epoxy resins include Epicoat 807 (manufactured by Mitsubishi Chemical Corporation) and YDF-170 (manufactured by Toto Kasei Co., Ltd.). Commercially available phenol novolac type epoxy resins include Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Corporation), and DEN-438 (manufactured by Dow Chemical Corporation). ) Etc. can be mentioned. Examples of commercially available o-cresol novolak type epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available polyphenol type epoxy resins include Epicoat 1032H60 and Epicoat YX-4000 (manufactured by Mitsubishi Chemical Corporation).

The epoxy equivalent of the epoxy resin (C) is preferably 100 to 500 g / eq, and more preferably 150 to 400 g / eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. Epoxy equivalents can be measured, for example, by the method specified in JISK7236.

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

When the curable resin composition of the present invention contains the epoxy resin (C), the content thereof is preferably 1 to 1 to 100 parts by mass with respect to the total content of the resin (A) and the reactive monomer (B) by 100 parts by mass. It is 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 obtained cured film tends to have excellent adhesion to the substrate.

<Polymer Initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used. ..
As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound is more preferable. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

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

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 -On-2-Imine can be mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA CORPORATION) may be used.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one Can be mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (all manufactured by BASF) may be used. Further, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-A-2002-544205, may be used. Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyldimethylketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftil) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) )-1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine Be done.

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

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, Japanese Patent Laid-Open No. 7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoyl compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinon compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate, and titanosen compounds. These are preferably used in combination with the polymerization initiation aid (D1) (particularly an amine compound) described later.

As the polymerization initiator (D), an acid generator can also be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyltosilates, Examples thereof include benzointosylate.

When the curable resin composition of the present invention contains a polymerization initiator (D), the content thereof is preferably 0 with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is 1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be increased and the exposure time tends to be shortened, so that the productivity is improved and the visible light transmittance of the obtained pattern tends to be high. There is.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is used together with the polymerization initiator (D) to promote the polymerization of the reactive monomer (for example, the (meth) acrylic compound (B1)) whose polymerization has been initiated by the polymerization initiator (D). It is a compound or a sensitizer used for the purpose.

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

Examples of the thiazolin compound include compounds represented by formulas (III-1) to (III-3), compounds described in JP-A-2008-6319, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, with 4,4'-bis (diethylamino) benzophenone being preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When the curable resin composition of the present invention contains a polymerization initiation aid (D1), the content thereof is preferably 100 parts by mass based on the total content of the resin (A) and the reactive monomer (B). It is 0.1 to 30 parts by mass, more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation aid (D1) is within the above range, the sensitivity tends to be higher when forming a pattern.

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

Examples of the thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanyl propionate), butanediol bis (3-sulfanyl acetate), and ethylene. Glycolbis (3-sulfanyl acetate), trimethylolpropanetris (3-sulfanylacetate), butanediol bis (3-sulfanylpropionate), trimethylolpropanetris (3-sulfanylpropionate), trimethylolpropanetris (3-sulfanylpropionate) 3-Sulfanyl Acetate), Pentaerythritol Tetrakiss (3-Sulfanyl Propionate), Pentaerythritol Tetrakiss (3-Sulfanyl Acetate), Trishydroxyethyl Tris (3-Sulfanyl Propionate), Pentaerythritol Tetrakiss (3-Sulfanyl Butyrate) ), 1,4-Bis (3-sulfanylbutyloxy) butane.

When the curable resin composition of the present invention contains a thiol compound (T), the content thereof is preferably 10 to 90 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the content of the polymerization initiator (D). It is 15 to 70 parts by mass. When the content of the thiol compound (T) is within the above range, the sensitivity tends to be 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 preferable because the cured film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 2- [1- (2-hydroxy). -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6- tert-Butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione, 3,3', 3 ", 5,5', 5" -Hexa-tert-butyl-a, a', a "-(mecitylene-2,4,6-triyl) tri- p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 6- [3-( 3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosfepine As the phenol-based antioxidant, a commercially available product may be used. Examples of the commercially available phenol-based antioxidant include Sumilyzer (registered trademark) BHT, GM, GS, GP (all of the above). Examples thereof include Sumitomo Chemical Co., Ltd.) and Irganox (registered trademark) 1010, 1076, 1330, 3114 (all manufactured by BASF).

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, disstearyl 3,3'-thiodipropionate, and pentaerythrityl tetrakis (3). -Laurylthiopropionate). As the sulfur-based antioxidant, a commercially available product may be used. Examples of commercially available sulfur-based antioxidants include Sumilyzer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tridecylphosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1, and so on. Examples thereof include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos (registered trademark) 168, 12, 38 (all manufactured by BASF), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). Be done.

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

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

<Surfactant (H)>
Examples of the surfactant (H) include a silicone-based surfactant having no fluorine atom, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond.
Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322. , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan) And so on.

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

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megafuck (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation). Preferred is Megafuck® F475.

When the curable resin composition of the present invention contains a surfactant (H), the content thereof is 0.001% by mass or more and 0.2% by mass or less with respect to the total amount of the curable resin composition of the present invention. It is preferably 0.002% by mass or more and 0.1% by mass or less, and 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 cured film can be improved.

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

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric acid anhydride, citraconic acid anhydride, itaconic acid anhydride, 2-dodecylsuccinic acid anhydride, 2- (2-octa-). 3-Enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarballylic acid anhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride Chain polyvalent carboxylic acid anhydrides such as those; 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6-tetrahydrophthalic acid anhydride, dimethyltetrahydrophthalic acid anhydride, hexahydrophthalate Acid Anhydride, 4-Methylhexahydrophthalic anhydride, Norbornendicarboxylic acid anhydride, Methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, Bicyclo [2.2.1] heptane- 2,3-Dicarboxylic Acid Anhydride, Bicyclo [2.2.1] Hepta-5-en-2,3-Dicarboxylic Acid Anhydride, Methylbicyclo [2.2.1] Hepta-5-en-2,3 -Alicyclic polyvalent carboxylic acid anhydrides such as dicarboxylic acid anhydrides and cyclopentanetetracarboxylic acid dianhydrides; phthalic anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, pyromellitic acid anhydride, Trimellitic acid anhydride, benzophenone tetracarboxylic acid dianhydride, 3,3'4,4'-diphenylsulfone tetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotrimeritate), glycerintris (anhydrotrimerite) Tate), Glycerinbis (Anhydrotrimericate) Monoacetate, 1,3,3a,4,5,9b-Hexahydro-5- (Tetrahydro-2,5-dioxo-3-franyl) Naft [1,2- c] Aromatic polyvalent carboxylic acid anhydrides such as furan-1,3-dione; Adeka Hardener-EH-700 (trade name (same below), manufactured by ADEKA Corporation), Ricacid-HH, same-TH, same-MH, same MH-700 (made by Shin Nihon Rika Co., Ltd.), Epikinia 126, same Commercially available products such as YH-306 and DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) may be used.

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

Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalent carboxylic acids are preferable because the cured film has excellent heat resistance and the transparency in the visible light region does not easily decrease. Acid anhydrides are more preferred.

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 reactive monomer (B). It is 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and further preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G) is within the above range, the heat resistance and adhesion of the cured film are excellent.

<Imidazole compound (J)>
The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Of these, the compound represented by the formula (2) is preferable.

[In the formula (1), 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 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group. The hydrogen atom contained in may be substituted with a hydroxy group. ]
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a heptadecyl group. , Undecyl group.

Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group and a cyanopentyl group.

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

Examples of the imidazole compound (J) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole and 2-ethylimidazole. , 2-Undecylimidazole, 2-Heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2- Hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole , 1-Cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4 -Methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole can be mentioned. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

When the curable resin composition of the present invention contains the imidazole compound (J), the content thereof is preferably 0. With respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is 1 part by mass or more and 25 parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, and further preferably 0.5 part by mass or more and 5 parts by mass or less. When the content of the imidazole compound (J) is in the above range, the obtained cured film tends to have excellent transparency in the visible light region.

<Solvent (E)>
The solvent (E) contains the solvent (E1) and may contain the solvent (E2). The solvent (E1) and the solvent (E2) are not particularly limited except that their boiling points are in different temperature ranges. The solvent (E1) has a boiling point of 200 ° C. or higher, preferably 220 ° C. or higher. The boiling point of the solvent (E1) is preferably 300 ° C. or lower. The solvent (E2) has a boiling point of less than 200 ° C. The boiling point of the solvent (E2) is preferably 100 ° C. or higher.

The solvent (E) contains 20% by mass or more of the solvent (E1). When the content of the solvent (E1) is in the above range, a cured film having a high surface flatness can be formed. The cured film is usually formed through a drying step of applying a curable resin composition to a substrate and then drying to form a composition layer, and a heating step of heating the composition layer to form a cured film. To. The curable resin composition of the present invention can form a cured film having a high surface flatness in the composition layer due to the action of the solvent remaining in the composition layer during the heating step. It is presumed that this is because the surface is easily flattened and the heating process is performed while the flattening is maintained. Further, it is presumed that by setting the content of the solvent (E1) in the above range, an appropriate amount of solvent for flattening can remain in the composition layer during the heating step. When the mass of the curable resin composition when applied to the substrate is 100, the mass of the composition layer subjected to the heating step of heating at a temperature of 30 ° C. or higher is preferably 30 or more, more preferably 30 or more. It is 40 or more, more preferably 60 or more, and it is preferable that the treatment is performed so that the mass is 20 or less by the heating step.

The curable resin composition of the present invention is prepared by applying a sample coated on a substrate so that the film thickness after heat treatment is 1.8 μm in a vacuum dryer under the condition of a temperature of 25 ° C. and a degree of decompression of 66 Pa. The curable resin composition was applied when the vacuum drying treatment for drying at a temperature of 100 ° C. for 3 minutes, the heat drying treatment for heating at a temperature of 230 ° C. for 30 minutes, and the heat treatment for heating at a temperature of 230 ° C. for 30 minutes were performed in order. Assuming that the mass of the sample immediately after is 100, the mass of the sample after the vacuum drying treatment and before the heat drying treatment is 30 or more, more preferably 40 or more, still more preferably 60 or more, and the heating. The mass of the treated sample is preferably 20 or less. When the curable resin composition satisfies such a numerical range, a cured film having a high surface flatness can be formed.

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

The content of the solvent (E2) in the solvent (E) can be 20% by mass or more and less than 80% by mass. The solvent (E2) contained in the solvent (E) preferably contains at least one of a solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C. (E2a) and a solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. (E2b). Those containing a solvent (E2a) are preferable. The content of the solvent (E2a) in the solvent (E) is preferably 10% by mass or more, more preferably 20% by mass or more.

When the solvent (E) contains the solvent (E1) and the solvent (E2), the average boiling point of the solvent (E1) contained in the solvent (E) and the average boiling point of the solvent (E2) contained in the solvent (E). The difference is preferably 80 ° C. or higher. Further, the average boiling point of the solvent (E2) contained in the solvent (E) is preferably 170 ° C. or lower. The average boiling point of a solvent is calculated from the boiling point of each solvent and its mass%. For example, the average boiling point of a solvent composed of 80% by mass of a solvent having a boiling point of 160 ° C. and 20% by mass of a solvent having a boiling point of 180 ° C. is 164 ° C. (= 160 ° C. × 0.8 + 180 ° C. × 0.2). The average boiling point of the solvent composed of 100% by mass of the solvent having a boiling point of 160 ° C. is 160 ° C.

The solvent (E1) is not particularly limited as long as the boiling point is 200 ° C. or higher, but is limited to triethylene glycol monobutyl ether (boiling point 283 ° C.), dipropylene glycol monopropyl ether (boiling point 213 ° C.), and diethylene glycol monoethyl ether (boiling point 202 ° C.). Ethereal solvents such as dipropylene glycol n-butyl ether (boiling point 229 ° C.), tripropylene glycol methyl ether (boiling point 242 ° C.), tripropylene glycol n-butyl ether (boiling point 274 ° C.);
1,2,3-Triacetoxypropane (boiling point 260 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C), 1,6-hexanediol diacetate (boiling point 260 ° C), 1,4-butanediol di Ester solvent such as acetate (boiling point 232 ° C);
Ether ester solvents such as diethylene glycol monobutyl ether acetate (boiling point 246.7 ° C), diethylene glycol monoethyl ether acetate (boiling point 217 ° C);
Alcoholic solvents such as 1,3 butylene glycol (boiling point 208 ° C.); and the like.

The solvent (E1) is at least one selected from the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane and triethylene glycol monobutyl ether. It is preferable to have.

The solvent (E2) is not particularly limited as long as the boiling point is less than 200 ° C., but is methoxybutanol (boiling point 161 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.), diethylene glycol diethyl ether (boiling point 189 ° C.), and diethylene glycol ethylmethyl ether (boiling point 189 ° C.). Dipropylene glycol dimethyl ether (boiling point 171 ° C), ethylene glycol monomethyl ether (boiling point 125 ° C), ethylene glycol monoethyl ether (boiling point 135 ° C.), propylene glycol monomethyl ether (boiling point 120 ° C.), propylene glycol monoethyl Ether solvents such as ether (boiling point 133 ° C.), propylene glycol monopropyl ether (boiling point 149 ° C.), diethylene glycol methyl ethyl ether (boiling point 176 ° C.);
Ester solvents such as methyl pyruvate (boiling point 138 ° C.), butyl propionate (boiling point 145 ° C.), methyl lactate (boiling point 155 ° C.), ethyl lactate (boiling point 155 ° C.), ethyl pyruvate (boiling point 144 ° C.);
Ketone solvents such as 2-heptanone (boiling point 151 ° C), 4-hydroxy-4-methyl-2-pentanone (boiling point 166 ° C), diisobutylketone (boiling point 168.4 ° C), cyclohexanone (boiling point 155 ° C);
Aromatic hydrocarbon solvents such as xylene (boiling point 144 ° C);
Alcoholic solvents such as 1-butanol (boiling point 117.6 ° C), 2-butanol (boiling point 98 ° C), isobutanol (boiling point 108 ° C);
3-methoxybutyl acetate (boiling point 172 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C), propylene glycol monoethyl ether acetate (boiling point 146 ° C), propylene glycol monomethyl ether propionate (boiling point 161 ° C), ethylene glycol monomethyl Ether ester solvents such as ether acetate (boiling point 144.5 ° C.), ethylene glycol monoethyl ether acetate (boiling point 156 ° C.), methyl 3-methoxypropionate (boiling point 142-143 ° C.);
Amide solvents such as N, N-dimethylformamide (boiling point 153 ° C.); and the like.

As the solvent (E2a), methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and ethylene glycol monomethyl ether acetate are preferable, and methoxybutanol and propylene glycol monoethyl ether acetate are used. Is more preferable.

As the solvent (E2b), diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, and 3-methoxybutyl acetate are preferable, and diethylene glycol methyl ethyl ether is more preferable.

The content of the solvent (E) is preferably 60 to 95% by mass, more 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 preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content of the solvent (E) is in the above range, the flatness of the film obtained by applying the curable resin composition tends to be high.

<Other ingredients>
The curable resin composition of the present invention is further known in the art as a filler, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters and the like, if necessary. May contain the additive of.

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

Adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy. Propylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyl Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, Examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

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

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

In the curable resin composition of the present invention, when a cured film is formed, the average transmittance of the cured film is preferably 90% or more, more preferably 95% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a cured film having a thickness of 2 μm after heat curing (100 to 250 ° C., 5 minutes to 3 hours). It is the average value when it is done. This makes it possible to provide a cured film having excellent transparency in the visible light region.

<Manufacturing method of curable resin composition>
The curable resin composition of the present invention contains the resin (A) and the solvent (E1), as well as the reactive monomer (B), the epoxy resin (C), the polymerization initiator (D), and the polymerization initiator contained as necessary. Auxiliary agent (D1), antioxidant (F), surfactant (H), polyvalent carboxylic acid (G), imidazole compound (J), solvent (E2) and other components are mixed by a known method. It can be manufactured by. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Manufacturing method of cured film>
The method for producing a cured film of the present invention includes a step of applying the above-mentioned curable resin composition of the present invention onto a substrate, and a step of heating the curable resin composition after coating. Usually, the cured film can be produced by applying the curable resin composition of the present invention on a substrate, drying the film, and then curing the film by heat. More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).
Step (1): Step of applying the curable resin composition of the present invention to the substrate Step (2): Step of drying the curable resin composition after coating under reduced pressure to form a composition layer (3): Step of Heating the Composition Layer Further, when the curable resin composition of the present invention contains the polymerization initiator (D), a cured film having a pattern can be produced by performing the following steps.
Step (1): Step of applying the curable resin composition of the present invention to the substrate Step (2): Step of drying the curable resin composition after coating under reduced pressure to form a composition layer (2a): Step of exposing the composition layer via a photomask (2b): Step of developing the exposed composition layer Step (3a): Step of heating the developed composition layer Step (1) is the present invention. This is a step of applying the curable resin composition of the present invention to a substrate. Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed on the substrate. The coating on the substrate is preferably performed using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

The step (2) is a step of drying the curable resin composition after coating 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 vacuum drying is preferably carried out under a pressure of 50 to 150 Pa and in a temperature range of 20 to 25 ° C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The temperature for heating and drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

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

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

From the viewpoint of improving the flatness of the cured film, the mass immediately after the application of the curable resin composition is 100, and the mass after prebaking in the step (2) is preferably 18 or more, more preferably 23 or more, and the step. (3) The mass after (3) is preferably 23 or less, more preferably 20 or less. The mass immediately after the curable resin composition is applied here is the mass in a state where the solvent does not evaporate, and is substantially the same as the mass of the curable resin composition used for the coating. Become.

The curable resin composition of the present invention is applied onto a substrate so that the film thickness after heat treatment is 1.8 μm, and dried in a vacuum drier under the condition of a temperature of 25 ° C. until the degree of decompression reaches 66 Pa. When the vacuum drying treatment, the heat drying treatment of heating at a temperature of 100 ° C. for 3 minutes, and the heat treatment of heating at a temperature of 230 ° C. for 30 minutes are performed in sequence, the mass of the curable resin composition immediately after application is 100. The mass of the curable resin composition film after the vacuum drying treatment and before the heat drying treatment is 30 or more, more preferably 40 or more, still more preferably 60 or more, and curing after the heat treatment. The mass of the resin composition film is preferably 20 or less. When the film obtained by each step satisfies the above numerical range, a cured film having a high surface flatness can be formed.

The step (2a) is a step of exposing the composition layer formed by the step (2) via a photomask. As the photomask, a photomask having a light-shielding portion formed corresponding to a portion of the composition layer to be removed is used. The shape of the light-shielding portion is not particularly limited and can be selected according to the intended use. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like.

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

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

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

Since the cured film thus obtained has excellent surface flatness, it is useful as a protective film or overcoat for, for example, a liquid crystal display device, an organic EL display device, a color filter substrate used for electronic paper, and a touch panel. .. This makes it possible to manufacture a display device provided with a high-quality cured film. Even in a color filter substrate having irregularities of a coloring pattern on the surface, the flatness of the surface can be improved by forming an overcoat with the curable resin composition of the present invention. The film thickness of the overcoat layer (the film thickness from the surface of the convex portion when the surface to be coated has irregularities) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. Preferably, when the surface to be coated has irregularities, it is preferably 30% or more of the height difference of the irregularities on the surface to be coated. According to the present invention, the flatness of the surface can be improved even by such a thin overcoat layer. By forming the overcoat layer with the curable resin composition of the present invention, the height difference of the unevenness on the surface of the overcoat layer can be 50% or less of the height difference of the unevenness of the surface to be coated.

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

[Examples 1 to 7 and Comparative Example 1]
<Preparation of curable resin composition>
Each component shown in Table 1 was mixed at the ratio shown in Table 1 to obtain a fluorine-based surfactant (Megafuck F554; manufactured by DIC Co., Ltd.) as an additive in order to further improve the waviness. A curable resin composition was obtained by adding 130 ppm to the total amount of the mixture.

In Table 1, the number of parts containing the resin (A) represents the parts by mass in terms of solid content, and the details of each component are as follows.

Resin (A): Resin (Aa) synthesized according to the following synthesis example 1.
Epoxy resin (C): Bisphenol A type epoxy resin (jER157S70; manufactured by Mitsubishi Chemical Corporation),
Reactive monomer (B): Monoallyl diglycidyl isocyanurate (MA-DGIC; manufactured by Shikoku Chemicals Corporation), which is a compound (B2).
Antioxidant (F) 1,3,5-Tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione (IRGANOX® 3114; manufactured by BASF), 1 part by mass of curable resin (A) and reactive monomer (B),
Polyvalent Carboxylic Acid (G): Butane Tetra Carboxylic Acid (Ricacid BT-W; manufactured by Shin Nihon Rika Co., Ltd.),
Adhesion promoter: N-phenyl-3-aminopropyltrimethoxysilane (silane coupling agent KBM573; Shin-Etsu Chemical Co., Ltd.),
Solvent (E1-1): 1,3-butylene glycol diacetate (BDGA) (boiling point 232 ° C),
Solvent (E1-2): Diethylene glycol monobutyl ether acetate (BDGAC) (boiling point 246.7 ° C.),
Solvent (E1-3): 1,6-hexanediol diacetate (1,6-HDDA) (boiling point 260 ° C.),
Solvent (E1-4): 1,2,3-triacetoxypropane (triacetin) (boiling point 260 ° C),
Solvent (E1-5): Triethylene glycol monobutyl ether (BTG) (boiling point 283 ° C.),
Solvent (E2-1): Diethylene glycol methyl ethyl ether (EDM) (boiling point 176 ° C.),
Solvent (E2-2): methoxybutanol (MB) (boiling point 161 ° C),
Solvent (E2-3): Propylene glycol monomethyl ether acetate (PGMA) (boiling point 146 ° C.).

The solvent (E) is mixed so that the solid content of the curable resin composition is 15% by mass, and the solvent components (E1-1) to (E1-5) and (E2-1) in the solvent (E) are mixed. The value of (E2-3) represents the mass ratio (%) in the solvent (E).

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

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethylmethyl ether was placed in a flask over 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (Aa)) having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the molecular weight distribution (Mw / Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH / g. It has the following structural units.

<Creation of evaluation board>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and isopropanol, and then dried. On this substrate, a colored photosensitive resin composition (solid content 19%; the solid content includes a pigment, an epoxy resin, an acrylic monomer, a polymerization initiator, an adhesion improver, and a surfactant in the following proportions). The film was spin-coated so that the film thickness after post-baking was 2.0 μm.
-Contents of each component in the colored photosensitive resin composition (ratio in solid content)
Pigment: Approximately 40% (Note: Ratio of green pigment in total amount of pigment: Approximately 90%, Yellow colorant in total amount of pigment: 10%), Epoxy resin: 3%, Acrylic monomer: 14%, Polymerization initiator: 10 %, Adhesion improver: 1%, Surfactant: 600 ppm
Next, a colored composition layer was formed by prebaking at 100 ° C. for 3 minutes in a clean oven. After allowing to cool, the distance between the colored composition layer on the substrate and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultrahigh pressure mercury lamp) is used in an atmospheric atmosphere. , 100 mJ / cm ² exposure (based on 365 nm). This light irradiation was performed by passing the synchrotron radiation from the ultrahigh pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a line-and-space pattern having a line width of 30 μm was used. The colored composition layer after light irradiation is developed by immersing it in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 60 seconds, washed with water, and then in an oven. In the middle, post-baking was performed at 230 ° C. for 30 minutes to prepare an evaluation substrate on which a line-and-space coloring pattern having a line width of 30 μm was formed.

The film thickness of the formed colored pattern was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.) with a measuring width of 500 μm and a measuring speed of 10 seconds to obtain a profile of the surface shape of the colored pattern. rice field. In addition, the average value of the film thickness of the coloring pattern was calculated from the profile. The average value of the film thickness was 2.0 μm.

<Creation of cured film>
The curable resin composition of Examples 1 to 7 and Comparative Example 1 was applied to the evaluation substrate by spin coating under the condition that the film thickness after post-baking (the film thickness from the surface of the colored pattern) was 1.0 μm. I applied the thing. After that, it was dried under a vacuum dryer (manufactured by VCD Microtech Co., Ltd.) under the conditions of a rotary pump rotation speed of 1000 rpm, a booster pump rotation speed of 700 rpm, and a room temperature of 25 ° C until the pressure reduction reached 66 Pa, and then dried on a hot plate. , Prebaked at a temperature of 100 ° C. for 3 minutes. After allowing to cool, a cured film was formed by post-baking at a temperature of 230 ° C. for 30 minutes.

The film thickness of the cured film on the evaluation substrate was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.) with a measuring width of 500 μm and a measuring speed of 10 seconds, and the profile of the surface shape of the cured film was measured. Got Moreover, when the average value of the film thickness of the cured film was calculated from the profile, the average value of the film thickness from the surface of the coloring pattern was 1.0 μm.

<Flatness evaluation>
1 and 2 show the outer shape of the coloring pattern of Example 1 and Comparative Example 1 and the profile of the surface shape of the cured film, respectively. The horizontal axis represents the position in the plane direction, and the vertical axis represents the position in the height direction. One protrusion in the profile of the outer surface shape of the tinted pattern corresponds to one tinted cell. In addition, the average height difference of the uneven pattern on the surface of the cured film was calculated from the profile of the outer surface shape of the obtained cured film. The results are shown in Table 1. When the height difference is 1.0 μm or less, the flatness of the cured film is good, and it can be said that it is particularly useful as a protective film for a color filter.
The height difference is more preferably 0.8 μm or less.

<Weight change>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and isopropanol, and then dried. The curable resin compositions of Examples 1 to 7 and Comparative Example 1 were spin-coated on this substrate so that the film thickness after post-baking was 1.8 μm. After that, in the process of preparing the cured film in the same process as the above-mentioned preparation of the cured film, the mass of the substrate immediately after the curable resin composition was applied (including the mass of the coated film) and the mass of the substrate after drying under reduced pressure (the mass of the substrate). The mass of the coating film (including the mass of the coating film), the mass of the substrate after prebaking (including the mass of the coating film), and the mass of the substrate after post-baking (including the mass of the cured film) were measured. The values obtained by subtracting the mass of the glass substrate from each measured value and converting the mass of the coating film immediately after coating the curable resin composition as 100 are shown in the “mass” column of Table 1, respectively.

As can be seen from the values shown in Table 1, the mass decreases as the process progresses, such as after drying, after pre-baking, and after post-baking, but the values related to the mass of the coating film after drying are those of each example. Was higher than the comparative example. It is understood that this is due to the evaporation of the solvent in the coating film. From the viewpoint of controlling the timing of evaporation of the solvent and improving the flatness of the cured film, the mass after vacuum drying is preferably 30 or more, and the mass after prebaking is preferably 18 or more, more preferably 23 or more. The mass after post-baking is preferably 23 or less, more preferably 20 or less. The mass immediately after the curable resin composition is applied here is the mass in a state where the solvent does not evaporate, and is substantially the same as the mass of the curable resin composition used for the coating. Become.

According to the present invention, it is possible to provide a curable resin composition capable of forming a cured film having a high surface flatness. Since the cured film obtained from the curable resin composition has excellent flatness, it can be suitably used for display devices and the like.

Claims (14)

Contains curable resins, solvents, and reactive monomers, and is substantially free of colorants.
The curable resin has a structural unit derived from at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and ethylene. Containing a copolymer containing a structural unit derived from a monomer having a sex unsaturated bond,
The solvent contains 20% by mass or more of the first solvent and contains 20% by mass or more.
The boiling point of the first solvent is 200 ° C. or higher, and the temperature is 200 ° C. or higher.
The first solvent is at least one selected from the group consisting of 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, 1,2,3-triacetoxypropane and triethylene glycol monobutyl ether. ,
The reactive monomer is a curable resin composition which is a compound having an acryloyl group, a compound having a methacryloyl group, or a compound represented by the following formula (1) .

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

[In formulas (a) and (b), R ⁴ and R ⁵ represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms independently of each other. ] "" The curable resin composition according to claim 1, wherein the solvent contains the first solvent in an amount of 20% by mass or more and 80% by mass or less. The curable resin composition according to claim 1 or 2, wherein the first solvent has a boiling point of 220 ° C. or higher. The solvent further contains a second solvent and
The curable resin composition according to any one of claims 1 to 3, wherein the boiling point of the second solvent is less than 200 ° C. The curable resin according to claim 4, wherein the second solvent is at least one selected from the group consisting of a solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C. and a solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. Composition. The second solvent contains the solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C.
The solvent having a boiling point of 100 ° C. or higher and lower than 170 ° C. is selected from the group consisting of methoxybutanol, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, and ethylene glycol monomethyl ether acetate. The curable resin composition according to claim 5, which is at least one kind. The second solvent contains the solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C.
The solvent having a boiling point of 170 ° C. or higher and lower than 200 ° C. is at least one selected from the group consisting of diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, and 3-methoxybutyl acetate. The curable resin composition according to claim 5 or 6. The curable resin composition according to any one of claims 1 to 7, which comprises at least one selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin, in addition to the curable resin. The curable resin composition according to any one of claims 1 to 8, further comprising an antioxidant. A curable resin composition containing a curable resin and a solvent.
A sample obtained by applying the curable resin composition on a substrate so that the film thickness after heat treatment is 1.8 μm is dried in a vacuum dryer under the condition of a temperature of 25 ° C. until the pressure reduction reaches 66 Pa. When the vacuum drying treatment for heating, the heat drying treatment for heating at a temperature of 100 ° C. for 3 minutes, and the heat treatment for heating at a temperature of 230 ° C. for 30 minutes are performed in sequence, the sample immediately after the application of the curable resin composition is performed. When the mass is 100, any one of claims 1 to 9, wherein the mass of the sample after the vacuum drying treatment and before the heat drying treatment is 30 or more, and the mass of the sample after the heat treatment is 20 or less. The curable resin composition according to the above. A cured film formed from the curable resin composition according to any one of claims 1 to 10. The cured film according to claim 11, which is a protective film for a color filter or a touch panel. A display device comprising the cured film according to claim 12. A method for producing a cured film, which comprises a step of applying the curable resin composition according to any one of claims 1 to 10 onto a substrate, and a step of heating the curable resin composition after coating.

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