JP6187010B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

  In recent liquid crystal display devices, a curable resin composition is used to form a cured film such as a photo spacer or an overcoat. As such a curable resin composition, only a copolymer of 3,4-epoxytricyclo [5.2.1.02,6] decyl acrylate and methacrylic acid having an epoxy equivalent of 500 g / eq or less is used as the resin. A composition containing the same is known (Patent Document 1).

JP 2010-202842 A

  In the conventionally proposed curable resin compositions, the adhesion between the obtained pattern and the substrate is not always satisfactory.

The present invention provides the following [1] to [6].
[1] A curable resin composition comprising a resin (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
Resin (A): a single unit having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A resin having a structural unit derived from a body and having an epoxy equivalent of 200 g / eq or more and 500 g / eq or less.
Resin (B): a single unit having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A resin having a structural unit derived from a body and having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less.
[2] The curable resin composition according to [1], wherein the content ratio of the resin (A) to the resin (B) is 30:70 to 80:20 on a mass basis.
[3] polymerization initiator comprises a biimidazole compounds and O- acyl oxime compound [1] or [2] The curable resin composition.
[4] A pattern formed using the curable resin composition according to any one of [1] to [3].
[5] A photospacer formed using the curable resin composition according to any one of [1] to [3].
[6] A display device comprising at least one selected from the group consisting of the pattern according to [4] and the photospacer according to [5].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition which can obtain the pattern excellent in adhesiveness with a board | substrate.

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

The curable resin composition of the present invention contains a resin (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
Resin (A): a single unit having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond Derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Resin (B) containing a structural unit derived from the body and having an epoxy equivalent of 200 g / eq to 500 g / eq And a structural unit derived from a monomer having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond, and having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less

  The curable resin composition of the present invention preferably contains an antioxidant (F) and / or a surfactant (H).

<Resin>
The resin used in the curable resin composition of the present invention is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter sometimes referred to as “(a)”). And a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”). The copolymer further comprises a structural unit that is copolymerizable with (a) and derived from a monomer different from (a) and (b) (hereinafter sometimes referred to as “(c)”). You may have.
The resin 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).

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

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

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

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

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

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), Formula (II) And the like.

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

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

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

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

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

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

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

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

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

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

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

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

  These resins can be produced by a known method (for example, radical polymerization method or the like). The obtained resin may be used for the preparation of the curable resin composition of the present invention as it is after the reaction, or may be a concentrated or diluted solution, and may be solid (powder) by a method such as reprecipitation. You may use what was taken out as. In particular, when the solvent used for the curable resin composition of the present invention is used for the production of the resin, the solution after the reaction can be used as it is for the production of the curable resin composition. The process can be simplified.

Among the resins described above, a resin having an epoxy equivalent of 200 g / eq to 500 g / eq is used as the resin (A), and a resin having an epoxy equivalent of 1200 g / eq to 2600 g / eq is used as the resin (B).
In order to control the epoxy equivalent within the above range, the ratio of the structural units derived from (b) is adjusted. That is, the epoxy equivalent is decreased by increasing the proportion of the structural unit derived from (b), and conversely, the epoxy equivalent tends to be increased by decreasing the proportion of the structural unit derived from (b).
Resin (A) consists of the resin mentioned above, and an epoxy equivalent is 200 g / eq or more and 500 g / eq or less, Preferably it is 220 g / eq or more and 400 g / eq or less.
The epoxy equivalent can be measured, for example, by the method defined in JIS K7236, preferably by the indicator titration method.

When the resin (A) is the resin [K1], the ratio of structural units derived from the respective monomers is based on the total structural units constituting the resin (A).
Structural unit derived from (a); 5-76 mol%
Structural unit derived from (b); 24-95 mol%
Is preferred,
Structural unit derived from (a); 5-68 mol%
Structural unit derived from (b); 32-95 mol%
Is more preferable.

When the resin (A) is the resin [K2], the ratio of the structural units derived from each is relative to all the structural units constituting the resin (A).
Structural unit derived from (a); 2 to 40 mol%
Structural unit derived from (b); 30-90 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5-35 mol%
Structural unit derived from (b); 35-90 mol%
Structural unit derived from (c); 1-60 mol%
It is more preferable that
When the ratio of the structural unit of the resin (A) is within the above range, the chemical resistance of the cured film tends to be excellent.

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

  The acid value of the resin (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, 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 necessary to neutralize 1 g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion to the substrate.

Resin (B) consists of the resin mentioned above, and an epoxy equivalent is 1200 g / eq or more and 2600 g / eq or less, Preferably it is 1400 g / eq or more and 2500 g / eq or less.
An epoxy equivalent is calculated | required by the method similar to the above.

The resin (B) is preferably resin [K2]. In this case, the ratio of the structural unit derived from each is relative to all the structural units constituting the resin (B).
Structural unit derived from (a); 4 to 40 mol%
Structural unit derived from (b); 1-10 mol%
Structural unit derived from (c); 50-95 mol%
It is preferable that
Structural unit derived from (a); 8-35 mol%
Structural unit derived from (b); 2-9 mol%
Structural unit derived from (c); 56-90 mol%
It is more preferable that
When the ratio of the structural unit of the resin (B) is within the above range, the resulting cured film tends to be excellent in heat resistance.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the weight average molecular weight of the resin (B) is within the above range, the applicability of the curable resin composition tends to be good.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the obtained cured film tends to be excellent in chemical resistance.

  The acid value of the resin (B) is preferably 30 mg-KOH / g or more and 220 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 215 mg-KOH / g or less, and further preferably 50 mg-KOH / g. It is 210 mg-KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion to the substrate.

  The curable resin composition of the present invention may contain a resin other than the resin (A) and the resin (B). In this case, the content of the resin other than the resin (A) and the resin (B) is preferably 1 to 30% by mass and more preferably 5 to 20% by mass with respect to the total amount of the resin.

The content ratio [resin (A): resin (B)] of resin (A) and resin (B) is preferably 30: 70-80: 20, more preferably 30: 70-70: 30, based on mass. It is.
The total amount of the resin is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and further preferably 40 to 70% by mass with respect to the solid content of the curable resin composition of the present invention.
When the total amount of the resin is within the above range, the obtained cured film tends to be excellent in heat resistance and excellent in adhesion to the substrate and chemical resistance. Here, solid content of curable resin composition means the quantity remove | excluding content of the solvent (E) from the total amount of the curable resin composition of this invention.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by active radicals generated from the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, preferably (meth). Acrylic ester compound.

  Examples of the polymerizable compound (C) having one ethylenically unsaturated bond include the same compounds as those described above as (a), (b) and (c), and among them, (meth) acrylic acid esters Is preferred.

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Of 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) a Relate, 3-methyl pentanediol di (meth) acrylate.

  Examples of polymerizable compounds having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylation. Trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (Meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol Rehepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripenta Erythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaeryth Tall hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, Caprolactone-modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone modification Examples include tripentaerythritol hepta (meth) acrylate and acid anhydrides.

Among these, a polymerizable compound having three or more ethylenically unsaturated bonds is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.
The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 to 1,500 or less.

  The content of the polymerizable compound (C) is preferably 5 to 69% by mass, more preferably 20 to 64% by mass, based on the total amount of the resin (A), the resin (B) and the polymerizable compound (C). It is. When the content of the polymerizable compound (C) is within the above range, the sensitivity at the time of preparing the resin pattern and the strength, smoothness and reliability of the resulting resin pattern or cured film tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acyl phosphine oxide compounds, and biimidazole compounds.

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

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

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

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

  Furthermore, as polymerization initiators, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'- Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethyl Examples include quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and O-acyloxy compounds. More preferred is a polymerization initiator containing a sulfur compound, and more preferred is a polymerization initiator containing an O-acyloxime compound and a biimidazole compound. These polymerization initiators tend to be highly sensitive and have high transmittance in the visible light region.
When the polymerization initiator (D) contains an O-acyl oxime compound, the content of the O-acyl oxime compound is preferably 30 to 100% by mass, more preferably, based on the total amount of the polymerization initiator (D). Is 60 to 100% by mass.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). It is 5-15 mass parts, More preferably, it is 1-8 mass parts. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity is improved and the visible light transmittance of the resulting resin pattern is high. Tend.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is used together with the polymerization initiator (D), and is used to promote the polymerization of the compound (for example, the polymerizable compound (C)) whose polymerization is initiated by the polymerization initiator (D). Or a sensitizer.

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

  Examples of the thiazoline compound include compounds represented by formula (III-1) to formula (III-3), compounds described in JP-A-2008-65319, 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-dimethylhexyl 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, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  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, 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 assistant (D1), the content thereof is preferably 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). It is 0.1-30 mass parts, More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (D1) is within the above range, the sensitivity tends to be higher when forming the resin pattern.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. Can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

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

  Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.

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

  Among the above-mentioned solvents, organic solvents having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and mixed solvents containing these are more preferred.

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

<Antioxidant (F)>
The curable resin composition of the present invention may contain an antioxidant (F).
Examples of the antioxidant (F) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among these, a phenolic antioxidant is preferable in that the cured film is less colored.

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

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

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

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

When the curable resin composition of the present invention contains an antioxidant (F), the content thereof is preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the total resin, More preferred is 1 part by mass or more. When the content of the antioxidant (F) is within the above range, the taper angle of the resulting pattern tends to increase.
<Surfactant (H)>
The curable resin composition of the present invention may contain a surfactant (H).
Examples of the surfactant (H) include silicone surfactants, fluorine surfactants, silicone surfactants having fluorine atoms, and the like.

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

Examples of the fluorosurfactant include surfactants having a fluorocarbon chain.
Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F489, F554, R30 (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

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

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

<Other ingredients>
If necessary, the curable resin composition of the present invention includes a filler, other polymer compound, a thermal radical generator, an ultraviolet absorber, a chain transfer agent, an adhesion promoter, an antioxidant, and the like in the technical field. May contain known additives.

Examples of the filler include glass, silica, and alumina.
Examples of other polymer compounds include thermosetting resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
Specific examples of the thermal radical generator include 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.
Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxyxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycol. Sidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino Ethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxy Silane etc. are mentioned.
Examples of the antioxidant include thermal acid generators described in JP 2010-152335 A.

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

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

The curable resin composition of the present invention comprises a resin (A), a resin (B), a polymerizable compound (C), a polymerizable initiator (D) and a solvent (E), and other additives as necessary. It can be produced by stirring and mixing by a conventionally known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

  The curable resin composition of the present invention forms, for example, a coating film by applying onto a substrate made of glass, metal, plastic or the like, a color filter, various insulating or conductive films, a drive circuit, or the like. can do. The coating film is preferably dried and cured. Moreover, the obtained coating film can be patterned into a desired shape and used as a pattern. Furthermore, these coating films or patterns may be formed and used as part of a component such as a display device.

First, the curable resin composition of the present invention is applied on a substrate.
As described above, the coating can be performed using various coating apparatuses such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, and a dip coater.

Then, it is preferable to dry or pre-bake to remove volatile components such as a solvent. Thereby, a smooth uncured coating film can be obtained.
The film thickness of the coating film in this case is not particularly limited, and can be appropriately adjusted depending on the material used, application, etc. For example, about 1 to 6 μm is exemplified.

Furthermore, the obtained uncured coating film is irradiated with light, for example, ultraviolet rays generated from a mercury lamp or a light emitting diode, through a mask for forming a target pattern. The shape of the mask at this time is not particularly limited, and various shapes can be mentioned. Further, the transmittance of the mask light transmitting portion is not particularly limited as long as it transmits light from the light source. The width and height of the pattern can be appropriately adjusted depending on the mask size, the transmittance of the mask light transmitting portion, and the like.
In recent exposure machines, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm is used using a bandpass filter that extracts these wavelength ranges. It is possible to selectively take out and irradiate parallel light uniformly on the entire exposure surface. At this time, an apparatus such as a mask aligner or a stepper may be used to accurately align the mask and the substrate.

Thereafter, a desired pattern shape can be obtained by bringing the coating film into contact with an aqueous alkali solution to dissolve a predetermined portion, for example, an unexposed portion, and developing.
The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.

The developer used for development is preferably an aqueous solution of an alkaline compound.
The alkaline compound may be either an inorganic or organic alkaline compound.
Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, Examples thereof include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned.
The density | concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.
The surfactant may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.

  Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecyl sodium sulfate. And alkylaryl sulfonates such as sodium naphthalene sulfonate.

Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and still more preferably 0.1 to 5% by mass.

  After development, washing may be performed, and post-baking may be performed as necessary. Post bake is preferably performed at a temperature range of 150 to 240 ° C. for 10 to 180 minutes.

  The coating film or pattern thus obtained is useful as, for example, a photospacer used in a liquid crystal display device or a patternable overcoat. Moreover, a hole can be formed by using the photomask for hole formation at the time of patterning exposure to an uncured coating film, and it is useful as an interlayer insulation film. Furthermore, a transparent film can be formed by performing only the whole surface exposure and heat curing or heat curing without using a photomask when exposing the uncured coating film. This transparent film is useful as an overcoat. Further, it can be used for a display device such as a touch panel. Thereby, it is possible to manufacture a display device having a high-quality coating film or pattern with a high yield.

  The curable resin composition of the present invention is a material for forming various films and patterns, for example, a transparent film, pattern, photospacer, overcoat, insulating film constituting a part of a color filter and / or an array substrate. It is suitable for forming liquid crystal alignment control protrusions, microlenses, coat layers and the like. Further, a color filter, an array substrate, or the like provided with these coating films or patterns as a part of its constituent parts, and a display device including these color filters and / or an array substrate, for example, a liquid crystal display device, an organic EL device It can be used for electronic paper.

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

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をジエチレングリコールエチルメチルエーテル２４０部に溶解させた溶液を、別の滴下ポンプを用いて５時間かけてフラスコ内に滴下した。重合開始剤溶液の滴下が終了した後、７０℃で４時間保持し、その後室温まで冷却して、固形分４２．３％の共重合体（樹脂Ａ）の溶液を得た。得られた樹脂Ａａの重量平均分子量は８０００、分子量分布は１．９１、固形分換算の酸価は６０ｍｇ−ＫＯＨ／ｇ、エポキシ当量は２５７ｇ／ｅｑであった。樹脂Ａは、下記の構造単位を有する。

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

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was placed in a flask over another 5 hours using another dropping pump. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a copolymer (resin A) solution having a solid content of 42.3%. The obtained resin Aa had a weight average molecular weight of 8,000, a molecular weight distribution of 1.91, an acid value in terms of solid content of 60 mg-KOH / g, and an epoxy equivalent of 257 g / eq. Resin A has the following structural units.

Synthesis example 2
An appropriate amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 248 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 63 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} 27 parts, 210 parts of methyl methacrylate and 195 parts of propylene glycol monomethyl ether acetate were added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 12 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 245 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin B) solution having a solid content of 31.0%. The obtained resin B had a weight average molecular weight of 24,500, a molecular weight distribution of 2.03, an acid value in terms of solid content of 146 mg-KOH / g, and an epoxy equivalent of 2268 g / eq. Resin Ba has the following structural units.

Synthesis example 3
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 81 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} 27 parts, 144 parts of styrene, 48 parts of methyl methacrylate and 184 parts of propylene glycol monomethyl ether acetate were added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 12 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 248 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the completion of dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin Ba) solution having a solid content of 31.0%. The obtained resin Ba had a weight average molecular weight of 21,000, a molecular weight distribution of 2.07, an acid value in terms of solid content of 185 mg-KOH / g, and an epoxy equivalent of 1985 g / eq. Resin Bb has the following structural units.

Synthesis example 4
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 240 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 81 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} 27 parts, 48 parts of styrene, 144 parts of methyl methacrylate and 172 parts of propylene glycol monomethyl ether acetate were added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 8 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 280 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Ba) solution having a solid content of 30.7%. The obtained resin Bc had a weight average molecular weight of 25730, a molecular weight distribution of 2.18, an acid value in terms of solid content of 176 mg-KOH / g, and an epoxy equivalent of 2058 g / eq. Resin Bc has the following structural units.

Synthesis example 5
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 240 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 87 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1)] = 50: 50} 27 parts, 93 parts of styrene, 93 parts of methyl methacrylate and 172 parts of propylene glycol monomethyl ether acetate were added dropwise over 4 hours. On the other hand, a mixed solution prepared by dissolving 8 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 280 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of dropping, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin Ba) solution having a solid content of 30.9%. The obtained resin Bd had a weight average molecular weight of 24090, a molecular weight distribution of 2.18, an acid value in terms of solid content of 184 mg-KOH / g, and an epoxy equivalent of 1886 g / eq. Resin Bd has the following structural units.

<Measurement of molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Ｂ：終点までの滴定に消費した０．１Ｎ臭化水素／酢酸溶液の量（mＬ）
Ｆ：０．１Ｎ臭化水素／酢酸溶液のファクター
Ｗ：滴定に用いた測定用試料の量（g）
Ｎ：上記で得られた樹脂溶液の固形分（％） <Measurement of epoxy equivalent>
0.2 g of the resin solution obtained above was precisely weighed into a 50 mL conical flask with a stopper, and 5 mL of toluene and 20 mL of acetic acid were added to prepare a measurement sample. The measurement sample was further added with 1 drop of 1% crystal violet / acetic acid solution as an indicator, and titrated with a 0.1N hydrogen bromide / acetic acid solution to obtain an epoxy equivalent [g / eq] according to the following formula. .

B: Amount of 0.1N hydrogen bromide / acetic acid solution consumed for titration to the end point (mL)
F: Factor of 0.1N hydrogen bromide / acetic acid solution
W: Amount of measurement sample used for titration (g)
N: Solid content (%) of the resin solution obtained above

Examples 1-4 and Comparative Examples 1-2
<Preparation of curable resin composition>
Each component shown in Table 1 was mixed in the ratio shown in Table 1 to obtain a curable resin composition.

In Table 1, the content of the resin (A) represents a mass part in terms of solid content.
Resin (A); Resin synthesized in Synthesis Example 1 Resin (Ba); Resin resin synthesized in Synthesis Example 2 (Bb); Resin resin synthesized in Synthesis Example 3 (Bc); Resin resin synthesized in Synthesis Example 4 ( Bd); resin synthesized in Synthesis Example 5 polymerizable compound (C); dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D); Da; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF; oxime compound)
Polymerization initiator (D); Db; 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (B-CIM; Hodogaya Chemical ( Made by Co., Ltd.)
Polymerization initiation aid (D1); 2,4-diethylthioxanthone (KAYACURE DE)
TX-S; manufactured by Nippon Kayaku Co., Ltd.); thioxanthone compound antioxidant (F); 4,4′-butane-1,1-diylbis (6-tert-butyl-m-cresol); ) BBM-S; manufactured by Sumitomo Chemical Co., Ltd.)
Surfactant (H); Ha; Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
Solvent (E); Ea; Diethylene glycol ethyl methyl ether Solvent (E); Eb; Propylene glycol monomethyl ether acetate Solvent (E); Ec; 3-methoxy-1-butanol Solvent (Ea) in solvent (E) The mass ratio of (Ee) was set to the value shown in Table 1, and the solvent (E) was mixed so that the solid content of the curable resin composition became “solid content (%)” of Table 1.

<Measurement of transmittance of composition>
About the obtained photosensitive resin composition, the average in 400-700 nm was respectively used for the ultraviolet visible near infrared spectrophotometer (V-650; JASCO Corporation make) (quartz cell, optical path length: 1 cm). The transmittance (%) was measured. The results are shown in Table 2.

<Production of cured film>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition is spin-coated so that the film thickness after post-baking is 3.0 μm, and until the degree of vacuum reaches 66 kPa with a vacuum dryer (manufactured by Microtech Co., Ltd.). After drying under reduced pressure, it was prebaked at 90 ° C. for 80 seconds on a hot plate and dried to form a composition layer. After standing to cool, the exposure amount was 60 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source; ultrahigh pressure mercury lamp). In addition, irradiation to the composition layer at this time was performed by passing the radiated light from the ultrahigh pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Spectroscopy Co., Ltd.). After the light irradiation, the exposed composition layer was immersed in an aqueous developer containing 0.18% nonionic surfactant and 0.06% potassium hydroxide at 25 ° C. for 60 seconds while being further washed. . Then, it heated for 15 minutes at 235 degreeC in oven, and obtained the cured film.

<Measurement of transmittance of cured film>
The average transmittance (%) at 400 to 700 nm was measured for the obtained cured film using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 2.
<Pattern formation method>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and isopropanol and then dried. A photosensitive resin composition is spin-coated on this glass substrate, and then the pressure is reduced to 66 Pa with a vacuum dryer, and then prebaked at 90 ° C. for 80 seconds on a hot plate to form a composition layer. did. After allowing to cool, the distance between the substrate on which the composition layer is formed and the quartz glass photomask is 150 μm, and exposure is performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp). Under an atmosphere, light having an exposure amount of 60 mJ / cm 2 (365 nm standard) was irradiated. In addition, irradiation to the composition layer at this time was performed by passing the radiated light from the ultrahigh pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Spectroscopy Co., Ltd.). In addition, as a photomask, a pattern (having square light-transmitting portions each having a side of 3 μm to 15 μm and having a square interval of 100 μm and 5600 pieces each) (that is, the light-transmitting portions) are coplanar. A halftone mask having two kinds of transmittances of 100% and 25% was used, using the photomask formed above.
After the light irradiation, the coating film was immersed in an aqueous developer containing 0.18% nonionic surfactant and 0.06% potassium hydroxide while shaking for 60 seconds at 25 ° C., and further washed with water. . Thereafter, post baking was performed in an oven at 235 ° C. for 15 minutes to obtain a resin pattern.

<Adhesion evaluation>
If the pattern obtained from the photomask pattern remains on the substrate without peeling with an optical microscope (Axio Imager MAT; manufactured by Carl Zeiss Co., Ltd.), the pattern obtained is peeled off. If it is, it is marked as x in Table 2. If a pattern obtained from a photomask pattern having a smaller size remains, it can be determined that the adhesion is good.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition which can manufacture the pattern which is excellent in adhesiveness. The obtained pattern can be suitably used for a display device.

Claims (6)

A curable resin composition comprising a resin (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
Resin (A): a single unit having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A resin having a structural unit derived from a body and having an epoxy equivalent of 200 g / eq or more and 500 g / eq or less.
Resin (B): a single unit having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A resin having a structural unit derived from a body and having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less.   The curable resin composition according to claim 1, wherein the content ratio of the resin (A) to the resin (B) is 30:70 to 80:20 on a mass basis. Polymerization initiator, according to claim 1 or claim 2 curable resin composition according comprising the biimidazole compounds and O- acyl oxime compound.   The pattern formed using the curable resin composition in any one of Claims 1-3.   The photospacer formed using the curable resin composition in any one of Claims 1-3.   A display device comprising at least one selected from the group consisting of the pattern according to claim 4 and the photospacer according to claim 5.