KR102021619B1 - Curable resin composition - Google Patents

Abstract

An object of this invention is to provide curable resin composition containing following resin (A), following resin (B), a polymeric compound (C), a polymerization initiator (D), and a solvent (E).
Resin (A); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin whose epoxy equivalent is 200 g / eq or more and 500 g / eq or less.
Resin (B); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less.

Description

Curable Resin Composition {CURABLE RESIN COMPOSITION}

The present invention relates to a curable resin composition.

In a recent liquid crystal display device, in order to form cured films, such as a photospacer and an overcoat, curable resin composition is used. As such a curable resin composition, a composition containing only a copolymer of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate and methacrylic acid having an epoxy equivalent of 500 g / eq or less is known. (JP2010-202842-A).

In the curable resin composition proposed conventionally, adhesiveness with the patterned coating film obtained and a board | substrate was not necessarily able to fully be satisfied.

This invention provides the following [1]-[6].

[1] Curable resin composition comprising the following resin (A), the following resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E).

Resin (A); A structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides,

Resin containing the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, and whose epoxy equivalent is 200 g / eq or more and 500 g / eq or less.

Resin (B); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin 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) and the resin (B) is 30:70 to 80:20 on a mass basis.

[3] The curable resin composition according to [1] or [2], wherein the polymerization initiator contains a biimidazole compound and an O-acyl oxime compound.

[4] A patterned coating film formed using the curable resin composition according to any one of [1] to [3].

[5] A photo spacer formed by using the curable resin composition according to any one of [1] to [3].

[6] A display device comprising at least one member selected from the group consisting of a patterned coating film as described in [4] and a photospacer as described in [5].

According to this invention, it becomes possible to provide the curable resin composition which can obtain the patterned coating film excellent in adhesiveness with a board | substrate.

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless it is rejected in particular.

The photosensitive resin composition of this invention contains the following resin (A), following resin (B), a polymeric compound (C), a polymerization initiator (C), and a solvent (E).

Resin (A); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin whose epoxy equivalent is 200 g / eq or more and 500 g / eq or less.

Resin (B); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less.

It is preferable that curable resin composition of this invention contains antioxidant (F) and / or surfactant (H).

<Resin>

Resin used for curable resin composition of this invention is a structural unit derived from at least 1 sort (s) (hereinafter may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. And a copolymer containing 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)"). This copolymer may further copolymerize with (a) and may further have a structural unit derived from the monomer (Hereinafter, it may be called "(c)") different from (a) and (b).

The said resin, Preferably, it is the following resin [K1] and resin [K2].

Resin [K1]: a copolymer of (a) and (b);

Resin [K2]: A copolymer of (a) with (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-cyclohexenedicarboxylic 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 Bicyclo unsaturated compounds containing carboxyl groups, such as [2.2.1] hept-2-ene and 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-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among these, (meth) acrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity and the solubility to aqueous alkali solution, and (meth) acrylic acid is more preferable.

In addition, in this specification, "(meth) acryloyl" shows at least 1 sort (s) chosen from the group which consists of acryloyl and methacryloyl. Notation, such as "(meth) acrylic acid" and "(meth) acrylate", has the same meaning.

(b) refers to a polymerizable compound having an ethylenically unsaturated bond with, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) . As for (b), the monomer which has a C2-C4 cyclic ether and a (meth) acryloyloxy group is preferable.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)") and a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter "( b2) ", and the monomer (b3) (Hereinafter, it may be called" (b3) ") which has a tetrahydrofuryl group and ethylenically unsaturated bond.

(b1) is, for example, a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") and an alicyclic unsaturated hydrocarbon having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon. The monomer (b1-2) (Hereinafter, it may be called "(b1-2)") which has a structure which has become, is mentioned.

As (b1-1), glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzyl glyco Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl 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 (glycidyloxymethyl) styrene, and the like. have.

(b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane [eg, seroxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cycloma A400; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cycloma M100; Daicel Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

[In the said Formula (I) and Formula (II), R <^b1> and R <^b2> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

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 the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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, and more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1 And a 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-, and more preferably a single bond, * -CH ₂ CH ₂ -O- may be mentioned. * Represents the number of bonds with O.

As a compound represented by general formula (I), the compound etc. which are represented by either of the following general formula (I-1)-general formula (I-15) are mentioned. Among them, the following general formulas (I-1), (I-3), (I-5), (I-7), (I-9) or (I-11) to (I-11) The compound represented by 15) is preferable, and the compound represented by the following general formula (I-1), general formula (I-7), general formula (I-9), or general formula (I-15) is more preferable.

As a compound represented by general formula (II), the compound etc. which are represented by either of the following general formula (II-1)-general formula (II-15) are mentioned. Especially, the following general formula (I1-1), general formula (II-3), general formula (II-5), general formula (II-7), general formula (II-9) or general formula (II-11) to general formula (II-) The compound represented by 15) is preferable, and the compound represented by the following general formula (II-1), general formula (II-7), general formula (II-9), or general formula (II-15) is more preferable.

The compound represented by general formula (I) and the compound represented by general formula (II) may be used independently, respectively and may use 2 or more types together. When using the compound represented by general formula (I) and the compound represented by general formula (II) together, these content ratios [the compound represented by general formula (I): the compound represented by general formula (II)] are preferable on a molar basis. Preferably it is 5: 95-95: 5, More preferably, it is 20: 80-80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) from the point which can improve reliability, such as heat resistance and chemical-resistance of the cured film obtained. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclo Hexyl (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"). In addition, it may be called "tricyclodecyl (meth) acrylate.", And tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the technical field, it is a common name to "dish) Copenpentenyl (meth) acrylate "), dicyclo Tanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (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 and 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-hydroxybi Cyclo [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-methyl Bicyclo [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-phenoxy Cycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bi Ratios of s (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Cyclo unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide And vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable in terms of copolymerization reactivity and heat resistance.

As a specific example of resin [K1], the compound represented by (meth) acrylic acid / general formula (I-1) may be abbreviated as "chemical formula (I-1)" hereafter. The same applies.), Copolymer of (meth) acrylic acid / formula (I-2), copolymer of (meth) acrylic acid / formula (I-3), (meth) acrylic acid / formula (I-4) Copolymer of (meth) acrylic acid / chemical formula (I-5), copolymer of (meth) acrylic acid / chemical formula (I-6), copolymer of (meth) acrylic acid / chemical 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 / chemical formula Copolymer of (I-11), copolymer of (meth) acrylic acid / chemical formula (I-12), copolymer of (meth) acrylic acid / chemical formula (I-13), (meth) acrylic acid / chemical formula (I-14) Copolymer of (meth) acrylic acid / copolymer of formula (I-15), (meth) a Copolymer of (meth) acrylic acid / (II-2), copolymer of (meth) acrylic acid / (II-3), copolymer of (meth) acrylic acid / chemical formula (II-1) II-4) copolymer, (meth) acrylic acid / copolymer of formula (II-5), (meth) acrylic acid / copolymer of formula (II-6), (meth) acrylic acid / formula (II-7) Copolymer, copolymer of (meth) acrylic acid / formula (II-8), copolymer of (meth) acrylic acid / formula (II-9), copolymer of (meth) acrylic acid / formula (II-10), (meth Copolymers of acrylic acid / formula (II-11), copolymers of (meth) acrylic acid / formula (II-12), copolymers of (meth) acrylic acid / formula (II-13), (meth) acrylic acid / formula ( II-14) copolymer, (meth) acrylic acid / copolymer of formula (II-15), (meth) acrylic acid / copolymer of formula (I-1) / formula (II-1), (meth) acrylic acid / Copolymer of formula (I-2) / formula (II-2), (meth) acrylic acid / formula (I-3) / Copolymer of formula (II-3), copolymer of (meth) acrylic acid / formula (I-4) / formula (II-4), (meth) acrylic acid / formula (I-5) / formula (II-5) Copolymers of (meth) acrylic acid / (I-6) / (II-6), copolymers of (meth) acrylic acid / (I-7) / (II-7), (meth ) Acrylic acid / copolymer of formula (I-8) / formula (II-8), (meth) acrylic acid / copolymer of formula (I-9) / formula (II-9), (meth) acrylic acid / formula (I -10) / copolymer of formula (II-10), (meth) acrylic acid / copolymer of formula (I-11) / copolymer of formula (II-11), (meth) acrylic acid / formula (I-12) / formula ( Copolymer of (II-12), copolymer of (meth) acrylic acid / formula (I-13) / formula (II-13), air of (meth) acrylic acid / formula (I-14) / formula (II-14) Copolymer, (meth) acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth) acrylic acid / copolymer of formula (I-1) / formula (I-7), (meth) acrylic acid / Formula (I -1) / copolymer of formula (II-7), crotonic acid / copolymer of formula (I-1), crotonic acid / copolymer of formula (I-2), crotonic acid / formula (I-3) Copolymer, copolymer of crotonic acid / chemical formula (I-4), copolymer of crotonic acid / chemical formula (I-5), copolymer of crotonic acid / chemical formula (I-6), crotonic acid / chemical formula (I-7) ), Copolymer of crotonic acid / chemical formula (I-8), copolymer of crotonic acid / chemical formula (I-9), copolymer of crotonic acid / chemical formula (I-10), crotonic acid / chemical 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 / formula (I-15) copolymer, crotonic acid / copolymer of formula (II-1), crotonic acid / copolymer of formula (II-2), crotonic acid / copolymer of formula (II-3), crotonic acid / Copolymer of formula (II-4), crotonic acid / copolymer of formula (II-5), crotonic acid / formula (II-6) Copolymer, copolymer of crotonic acid / chemical formula (II-7), copolymer of crotonic acid / chemical formula (II-8), copolymer of crotonic acid / chemical formula (II-9), crotonic acid / chemical formula (II-10 ), Copolymer of crotonic acid / chemical formula (II-11), copolymer of crotonic acid / chemical formula (II-12), copolymer of crotonic acid / chemical formula (II-13), crotonic acid / chemical formula (II -14) copolymer, crotonic acid / copolymer of formula (II-15), maleic acid / copolymer of formula (I-1), maleic acid / copolymer of formula (I-2), maleic acid / formula Copolymer of (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), maleic acid / copolymer of formula (I-10), Maleic acid / copolymer of formula (I-11), maleic acid / copolymer of formula (I-12), maleic acid / copolymer of formula (I-13) Copolymer, maleic acid / copolymer of formula (I-14), maleic acid / copolymer of formula (I-15), maleic acid / copolymer of formula (II-1), maleic acid / formula (II-2) Copolymer of maleic acid / formula (II-3), copolymer of maleic acid / formula (II-4), copolymer of maleic acid / formula (II-5), maleic acid / formula (II- 6) copolymer, maleic acid / copolymer of formula (II-7), maleic acid / copolymer of formula (II-8), maleic acid / copolymer of formula (II-9), maleic acid / chemical formula ( II-10) copolymer, maleic acid / copolymer of formula (II-11), maleic acid / copolymer of formula (II-12), maleic acid / copolymer of formula (II-13), maleic acid / Copolymer of formula (II-14), copolymer of maleic acid / formula (II-15), copolymer of (meth) acrylic acid / maleic anhydride / formula 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) arc Copolymer of acid / maleic anhydride / formula (I-4), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-5), (meth) acrylic acid / maleic anhydride / formula (I-6) Copolymer of (meth) acrylic acid / maleic anhydride / (I-7), copolymer of (meth) acrylic acid / maleic anhydride / (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 / copolymer of formula (I-11), ( (Meth) acrylic acid / maleic anhydride / copolymer of formula (I-12), (meth) acrylic acid / maleic anhydride / copolymer of formula (I-13), (meth) acrylic acid / maleic anhydride / chemical formula (I- 14) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-15), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1), (meth) acrylic acid / male Acid Anhydride / Chemistry Copolymer of formula (II-2), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-3), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-4), (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 / formula (II-7) Copolymer of (meth) acrylic acid / maleic anhydride / (II-8), copolymer of (meth) acrylic acid / maleic anhydride / (II-9), (meth) acrylic acid / maleic acid Anhydride / copolymer of formula (II-10), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-11), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-12), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-13), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-14), (meth) acrylic acid / maleic anhydride / chemical formula (II -15) balls There may be mentioned copolymers and the like.

Specific examples of the resin [K2] include copolymers of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate and (meth) acrylic acid / formula (I-2) / methyl (meth) acrylate. Copolymer, copolymer of (meth) acrylic acid / formula (I-3) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-4) / methyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (I-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-6) / methyl (meth) acrylate, (meth) acrylic acid / formula (I- 7) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-8) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-9) / methyl (meth Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (I-10) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-11) / methyl (meth) acrylate , (Met) Copolymer of methacrylic acid / formula (I-12) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, (meth) acrylic acid / formula (I -14) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-15) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl ( Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-2) / methyl (meth) acrylate, air of (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 / Copolymer of formula (II-6) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-7) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-8 ) Copolymer of (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-9) / methyl (meth) acrylate, of (meth) acrylic acid / formula (II-10) / methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-12) / methyl (meth) acrylate, (meth) Copolymer of acrylic acid / formula (II-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-14) / methyl (meth) acrylate, (meth) acrylic acid / formula (II- 15) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / Dish Copolymer of clofentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / dicyclopentanyl (meth) acrylate, Copolymer of acid / formula (I-1) / dicyclopentanyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (I-1) / dicyclopentanyl (meth) acrylate, air of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylate Copolymer, copolymer of crotonic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid Copolymer of / maleic anhydride / formula (II-1) / dicyclopentanyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / dicyclopentanyl (meth) acrylic Copolymer of rate, (meth) acrylic acid / Formula (I-1) / Copolymer of phenyl (meth) acrylate, (meth) acrylic acid / Formula (I I-1) / Copolymer of phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / copolymer of formula (II-1) / phenyl (meth) acrylate, crotonic acid / formula (I -1) / copolymer of phenyl (meth) acrylate, maleic acid / formula (I-1) / copolymer of phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I-1) / Copolymer of phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / phenyl (meth) acrylate, crotonic acid / formula (II-1) / phenyl Copolymer of (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylic Copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylate, of (meth) acrylic acid / formula (I-1) / diethyl maleate Copolymer, Copolymer of (meth) acrylic acid / formula (II-1) / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / diethyl maleate, crotonic acid / formula ( Copolymer of I-1) / diethyl maleate, copolymer of maleic acid / formula (I-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / formula (I-1) / diethyl maleate Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate, copolymer of crotonic acid / formula (II-1) / diethyl maleate, maleic acid / formula ( Copolymer of II-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (II-1) / methyl (meth Copolymer of acrylate / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / 2 Hydroxyethyl (meth) acrylate Copolymer of meth, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (I-1) / 2- Copolymer of hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (I-1 Copolymer of (2) -hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, croton Copolymer of acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) Copolymer of acrylic acid / maleic anhydride / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxy Ethyl (meth) acrylic Copolymer of meth, copolymer of (meth) acrylic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (II-1) / bicyclo [2.2. 1] copolymer of hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / bicyclo [2.2.1] hept-2-ene, crotonic acid / formula Copolymer of (I-1) / bicyclo [2.2.1] hept-2-ene, copolymer of maleic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth ) Acrylic acid / maleic anhydride / copolymer of formula (I-1) / bicyclo [2.2.1] hept-2-ene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / r Copolymer of cyclo [2.2.1] hept-2-ene, copolymer of crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene, maleic acid / formula (II-1) Copolymer of /bicyclo[2.2.1]hept-2-ene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / bicyclo [2.2.1] hept-2-ene, ( (Meth) acrylic acid / formula (II-1) / methyl (meth) acrylic Copolymer of yttrate / bicyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II-1 ) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / Formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, crotonic acid / Formula (I-1) Copolymer of / N-cyclohexyl maleimide, copolymer of maleic acid / formula (I-1) / N-cyclohexyl maleimide, (meth) acrylic acid / maleic anhydride / formula (I-1) / N-cyclo Copolymer of hexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, crotonic acid / formula (II-1) / N-cyclohexyl Copolymer of maleimide, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, air of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide Copolymer, (meth) acrylic Copolymer of acid / chemical formula (II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / chemical formula (I-1) / styrene, (meth) acrylic acid / chemical formula ( II-1) / copolymer of styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymer of crotonic acid / formula (I-1) / styrene, male Copolymer of acid / formula (I-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) Copolymer of acrylate / styrene, copolymer of crotonic acid / formula (II-1) / styrene, copolymer of maleic acid / formula (II-1) / styrene, (meth) acrylic acid / maleic anhydride / formula ( Copolymer of (II-1) / styrene, (meth) acrylic acid / formula of (II-1) / methyl (meth) acrylate / styrene, (meth) acrylic acid / formula (I-1) / N-cyclohexyl Copolymer of maleimide / styrene, (meth ) A copolymer of acrylic acid / chemical formula (II-1) / N-cyclohexyl maleimide / styrene, (meth) acrylic acid / chemical formula (I-1) / chemical formula (II-1) / N-cyclohexyl maleimide / styrene Copolymer, copolymer of crotonic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, copolymer of maleic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) Copolymer of acrylic acid / maleic anhydride / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide Copolymer of / styrene, copolymer of crotonic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide / styrene, Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / N-C The copolymer of clohexyl maleimide / styrene, etc. are mentioned.

These resins can be manufactured by a well-known method (for example, radical polymerization method etc.). The obtained resin may use the solution after reaction as it is for preparation of curable resin composition of this invention, may use the concentrated or diluted solution, and what was taken out as solid (powder) by methods, such as reprecipitation, using Also good. In particular, when the solvent used for the curable resin composition of this invention is used for manufacture of resin, since the solution after reaction can be used as it is for manufacture of curable resin composition, the manufacturing process of curable resin composition can be simplified.

Among the resins described above, a resin having an epoxy equivalent of 200 g / eq or more and 500 g / eq or less is used as the resin (A), and a resin having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less is used as the resin (B), respectively. .

In order to control an epoxy equivalent in the said range, the ratio of the structural unit derived from (b) is adjusted. That is, epoxy equivalent becomes small by increasing the ratio of the structural unit derived from (b), and epoxy equivalent tends to become large by reducing the ratio of the structural unit derived from (b).

Resin (A) consists of resin mentioned above, and 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.

Epoxy equivalent weight can be measured, for example by the method prescribed | regulated to JISK7236, Preferably indicator titration method.

When resin (A) is resin [K1], the ratio of the structural unit derived from each monomer is with respect to the whole structural unit which comprises resin (A),

structural unit derived from (a); 5-76 mol%

structural unit derived from (b); 24-95 mol% is preferable,

structural unit derived from (a); 5-68 mol%

structural unit derived from (b); 32-95 mol% is more preferable.

When resin (A) is resin [K2], the ratio of the structural unit derived from each is with respect to the whole structural unit which comprises resin (A),

structural unit derived from (a); 2-40 mol%

structural unit derived from (b); 30 to 90 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5 to 35 mol%

structural unit derived from (b); 35 to 90 mol%

structural unit derived from (c); It is more preferable that it is 1-60 mol%.

When the ratio of the structural unit of resin (A) exists in the said range, it exists in the tendency for the chemical-resistance of a cured film to be excellent.

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-20,000, Especially preferably, it is 5,000-10,000. When the weight average molecular weight of resin (A) exists in the said range, there exists a tendency for the coating property of curable resin composition to become favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When the molecular weight distribution is in the above range, the cured film obtained 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, still more preferably 50 mg-KOH / g or more and 135 mg-KOH / g or less. 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 titration using an aqueous potassium hydroxide solution. When the acid value of resin (A) exists in the said range, the cured film obtained tends to be excellent in adhesiveness with a board | substrate.

Resin (B) consists of resin mentioned above, and epoxy equivalent is 1200 g / eq or more and 2600 g / eq or less, Preferably they are 1400 g / eq or more and 2500 g / eq or less.

Epoxy equivalent can be calculated | required by the same method as the above.

It is preferable that resin (B) is resin [K2]. In this case, the ratio of the structural unit derived from each is with respect to all the structural units which comprise resin (B),

structural unit derived from (a); 4-40 mol%

structural unit derived from (b); 1 to 10 mol%

structural unit derived from (c); It is preferable that it is 50-95 mol%,

structural unit derived from (a); 8 to 35 mol%

structural unit derived from (b); 2-9 mol%

structural unit derived from (c); It is more preferable that it is 56-90 mol%.

If the ratio of the structural unit of resin (B) exists in the said range, the cured film obtained will tend to be excellent in heat resistance.

The weight average molecular weight of polystyrene conversion of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the weight average molecular weight of resin (B) exists in the said range, there exists a tendency for the coating property of curable resin composition to become favorable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When the molecular weight distribution is in the above range, the cured film obtained 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, still more preferably 50 mg-KOH / g or more and 210 mg-KOH / g or less. 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 resin (A) exists in the said range, the cured film obtained tends to be excellent in adhesiveness with a board | substrate.

Curable resin composition of this invention may contain resin other than resin (A) and resin (B). In this case, content of resin other than resin (A) and resin (B) becomes like this. Preferably it is 1-30 mass% with respect to the total amount of resin, More preferably, it is 5-20 mass%.

The content ratio [resin (A): resin (B)] of the resin (A) and the resin (B) is preferably 30:70 to 80:20, more preferably 30:70 to 70:30 on a mass basis. .

The total amount of the resin is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 70% by mass with respect to the solid content of the curable resin composition of the present invention.

If the total amount of resin exists in the said range, the cured film obtained will be excellent in heat resistance and also tend to be excellent in adhesiveness with a board | substrate, and chemical-resistance. Here, solid content of curable resin composition means the quantity which removed content of the solvent (E) from the total amount of curable resin composition of this invention.

<Polymeric Compound (C)>

A polymerizable compound (C) is a compound which can superpose | polymerize with the active radical which generate | occur | produced from the polymerization initiator (D), For example, it is a compound etc. which have a polymerizable ethylenically unsaturated bond, Preferably it is a (meth) acrylic acid ester compound. .

As a polymeric compound (C) which has one ethylenically unsaturated bond, the thing similar to the compound mentioned as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is desirable.

Polymerizable compounds having two ethylenically unsaturated bonds include 1,3-butanedioldi (meth) acrylate, 1,3-butanediol (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, and ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol Diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, ethoxylated neopentylglycol di (meth) Acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylic acid. Ethoxylated 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, tripentaerythritolhepta (meth) acrylate, tripentaerythritol octa (Meth) acrylate, reactant of pentaerythritol tri (meth) acrylate with acid anhydride, diphene Reaction product of taerythritol penta (meth) acrylate with acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylic acid Latex, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, capro Lactone-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 tripentaerythritolhepta (meth) arc Latex, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and reactants of acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride A reactant, a caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned.

Especially, the polymeric compound which has 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, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably 5 to 69 mass%, more preferably 20 to 64 mass% with respect to the total amount of the resin (A), the resin (B) and the polymerizable compound (C). . When content of a polymeric compound (C) exists in said range, there exists a tendency for the sensitivity at the time of preparation of a resin patterned coating film, the strength, smoothness, and reliability of the resin patterned coating film and cured film obtained to become favorable.

<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 can initiate polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and biimidazole compounds.

The said O-acyl oxime compound is a compound which has the partial structure represented by general formula (d1). Hereinafter, * represents a bond number.

Examples of the O-acyl oxime 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-methyl Benzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-one-2-imine, etc. are mentioned. You may use commercially available products, such as Irgacure (trademark) OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation).

The alkylphenone compound is a compound having a partial structure represented by the general formula (d2) or a partial structure represented by the general 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 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane- 1-one etc. are mentioned. You may use commercial items, such as Irgacure (trademark) 369, 907, and 379 (above, BASF Corporation make). Moreover, you may use the polymerization initiator which has group which can cause chain transfer as described in JP2002-544205-A.

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- Oligomer of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α and? -diethoxyacetophenone, benzyl dimethyl ketal and the like.

In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by the general formula (d2) is preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

2,4,6-trimethylbenzoyldiphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use a commercial item, such as Irgacure (trademark) 819 (made by BASF Corporation).

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, eg, JPH06-75372-A, JPH06-75373-A, etc.), 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 (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4 ', 5,5'-position is substituted by carboalkoxy group The imidazole compound (for example, JPH07-10913-A etc.) etc. are mentioned.

Moreover, as a polymerization initiator, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4- Acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl Onium salts such as iodonium hexafluoroantimonate, nitrobenzyl tosylates, benzointosylates and the like.

As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound and a biimidazole compound is preferable, and O- The polymerization initiator containing an acyl oxime compound is more preferable, and the polymerization initiator containing a biimidazole compound and an O-acyl oxime compound is more preferable. If it is these polymerization initiators, it is highly sensitive and there exists a tendency for the transmittance | permeability in a visible light region to become high.

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 60 to the total amount of the polymerization initiator (D). It is -100 mass%.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). More preferably, it is 1-8 mass parts. When content of a polymerization initiator (D) exists in the said range, since it exists in the tendency to become high sensitivity and shorten an exposure time, productivity improves and there exists a tendency for the visible light transmittance of the resin patterned coating film obtained to be high.

<Polymerization start preparation (D1)>

A polymerization start adjuvant (D1) is used together with a polymerization initiator (D), and the compound used in order to accelerate superposition | polymerization of the compound (for example, a polymeric compound (C)) in which superposition | polymerization was started by the polymerization initiator (D), or It is a sensitizer.

As a polymerization start adjuvant (D1), a thiazoline compound, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and a carboxylic acid compound are mentioned, for example.

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic isoamyl acid, benzoic acid 2-dimethylaminoethyl, 4-dimethyl Aminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (ethylmethylamino) benzophenone etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy Citioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

When curable resin composition of this invention contains a polymerization start adjuvant (D1), the content becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total content of resin (A) and a polymeric compound (C). More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (D1) is within the above-described range, there is a tendency to become more sensitive when the resin patterned coating film is formed.

<Solvent (E)>

Solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and no -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), an ether ester solvent ( Solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcoholic solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide It can select from etc., and can use.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, 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.

As the ether solvent, 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, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole Etc. can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, and methyl 3-ethoxy propionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene glycol monobutyl ether acetate.

As ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo Pentanone, cyclohexanone, isophorone, etc. are mentioned.

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

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

Among the solvents described above, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm from the viewpoint of applicability and dryness are preferable, and among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and diethylene glycol Methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and mixed solvents containing them are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of curable resin composition of this invention, More preferably, it is 70-95 mass%. In other words, solid content of curable resin composition of this invention becomes like this. Preferably it is 5-40 mass%, More preferably, it is 5-30 mass%. When content of a solvent (E) exists in the said range, there exists a tendency for the flatness of the film | membrane which apply | coated curable resin composition to be high.

Antioxidant (F)

Curable resin composition of this invention may contain antioxidant (F).

As antioxidant (F), a phenolic antioxidant, sulfur type antioxidant, phosphorus antioxidant, and an amine antioxidant are mentioned. Especially, a phenolic antioxidant is preferable at the point that coloring of a cured film is few.

Phenolic antioxidants include, for example, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy- 3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 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- Methylphenol), 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 "-(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] dioxaphosphine, 4,4'-butane-1,1-diylbis (6-tert-butyl -m-cresol) etc. are mentioned.

You may use a commercial item as said phenolic antioxidant. Commercially available phenolic antioxidants include, for example, Sumerizer (registered trademark) BHT, GM, GS, GP, BBM-S (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all are the BASF Corporation make), etc. are mentioned.

Sulfur-based antioxidants include, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythritol Tetrakis (3-laurylthiopropionate) and the like. You may use a commercial item as said sulfur type antioxidant. Commercially available sulfur-based antioxidants include, for example, Sumerizer® TPL-R, TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Phosphorus antioxidants include, for example, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1,3- Tris (2-methyl-5-tert- butyl- 4-hydroxyphenyl) butanediphosphite etc. are mentioned. You may use a commercial item as said phosphorus antioxidant. Commercially available phosphorus antioxidants include Irgafos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), Adecastab 329K, Adecastab PEP36 (all manufactured by ADEKA), and the like. have.

As the amine antioxidant, for example, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, N, N'-dicyclohexyl- p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, etc. are mentioned. You may use a commercial item as said amine antioxidant. Commercially available amine antioxidants include, for example, Sumerizer® BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.) and the like.

When curable resin composition of this invention contains antioxidant (F), 0.05 mass part or more and 2 mass parts or less are preferable with respect to 100 mass parts of total amounts of resin, and 0.1 mass part or more and 1 mass part or less Is more preferable. When content of antioxidant (F) exists in the said range, there exists a tendency for the taper angle of the patterned coating film obtained to become large.

<Surfactant (H)>

Curable resin composition of this invention may contain surfactant (H).

As surfactant (H), silicone type surfactant, a fluorine type surfactant, silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

Silicone surfactants include surfactants having siloxane bonds.

Specifically, doray silicon DC3PA, doray silicon SH7PA, doray silicon DC11PA, doray silicon SH21PA, doray silicon SH28PA, doray silicon SH29PA, doray silicon SH30PA, polyether modified silicone oil SH8400 [brand name: doray silicon Dow Corning Corporation], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 ( Momentive Performance Materials Japan Co., Ltd.).

Examples of the fluorine-based surfactants include surfactants having a fluorocarbon chain.

Specifically, Florinate® FC430, Florinate FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapack® F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Megapack F489, Megapack F554, Megapack R30 (manufactured by DIC Corporation), F-Top® EF301, F-top EF303, F-top EF351, F-top EF352 [Mitsubishi Material Density Corporation Manufacture], Supron (trademark) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical 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 Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, and Mega Pack F443 (manufactured by DIC Corporation).

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

<Other ingredients>

The curable resin composition of this invention may contain additives known in the said technical field, such as a filler, another high molecular compound, a thermal radical generating agent, a ultraviolet absorber, a chain transfer agent, an adhesion promoter, and antioxidant, as needed. .

Glass, silica, alumina, etc. are mentioned as a filler.

As another high molecular compound, thermosetting resins, such as maleimide resin, thermoplastic resins, such as polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkylacrylate, polyester, and polyurethane, etc. are mentioned.

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 absorbent 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.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 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-fe Nyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyl triethoxysilane, etc. are mentioned.

As antioxidant, the thermal acid generator of Unexamined-Japanese-Patent No. 2010-152335 is mentioned, for example.

Curable resin composition of this invention does not contain coloring agents, such as a pigment and dye, substantially. That is, in the curable resin composition of this invention, the content of the coloring agent with respect to the whole composition is normally less than 1 mass%, Preferably it is less than 0.5 mass%.

Moreover, when curable resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and the transmittance | permeability was measured on the conditions of 400-700 nm of measurement wavelength using the spectrophotometer, average transmittance becomes like this. Preferably it is 70% It is above, More preferably, it is 80% or more.

Curable resin composition of this invention uses resin (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and other additives as needed by a conventionally well-known method. It can manufacture by stirring and mixing. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 µm to 1.0 µm.

Curable resin composition of this invention can form a coating film, for example by apply | coating on these board | substrates which formed board | substrates, such as glass, a metal, and plastics, color filters, various insulation or electrically conductive films, a drive circuit, etc. It is preferable that the coating film was dried and hardened | cured. Moreover, the obtained coating film can also be patterned to a desired shape, and can also be used as a patterning coating film. In addition, you may form and use these coating films or a patterned coating film as a part of component parts, such as a display apparatus.

First, the curable resin composition of this invention is apply | coated on a board | substrate.

Application | coating can be performed using various coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

Then, it is preferable to dry or prebak and 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 specifically limited, It can adjust suitably according to the material, a use, etc. which are used, For example, about 1-6 micrometers is illustrated.

In addition, the obtained uncured coating film is irradiated with light, for example, mercury lamp, ultraviolet rays generated from a light emitting diode, or the like through a mask for forming a desired patterned coating film. The shape of the mask at this time is not specifically limited, Various shapes are 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, height, etc. of a pattern can be adjusted suitably according to the mask size, the transmittance | permeability of a mask light-transmitting part, etc ..

In the recent exposure machine, the band | pass filter which cuts the light of less than 350 nm using the filter which cuts this wavelength range, or extracts these wavelength ranges the light of 436 nm vicinity, 408 nm vicinity, and 365 nm vicinity is used. It can take out selectively, and irradiates a parallel light beam uniformly to the whole exposure surface. At this time, a device such as a mask aligner, a stepper, or the like may be used in order to accurately position the mask and the substrate.

Thereafter, the coating film is brought into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, such as a non-exposed portion, to obtain a target pattern shape.

The developing method may be any of a paddle method, a dipping method, a spray method and the like. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

As for the developing solution used for image development, the aqueous solution of an alkaline compound is preferable.

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, sodium carbonate, potassium carbonate, hydrogen carbonate Sodium, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like.

As the organic alkaline compound, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoiso Propylamine, diisopropylamine, ethanolamine and the like.

The 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 said alkaline compound may contain surfactant.

The surfactant may be any of a nonionic surfactant, anionic surfactant, or cationic surfactant.

Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkylaryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxy Ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Anionic surfactants include, for example, higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate or sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate or ammonium lauryl sulfate, sodium dodecylbenzenesulfonate or dodecyl. Alkyl aryl sulfonates, such as sodium naphthalene sulfonate, etc. are mentioned.

Examples of the cationic surfactants include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride or quaternary ammonium salts.

The density | concentration of surfactant in alkaline developing solution becomes like this. Preferably it is the range of 0.01-10 mass%, More preferably, it is 0.05-8 mass%, More preferably, it is 0.1-5 mass%.

After image development, water washing may be performed and post-baking may be further performed as needed. It is preferable to perform post-baking for 10 to 180 minutes in 150 degreeC-240 degreeC temperature range.

The coating film or patterned coating film obtained in this way is useful as a photospacer used for a liquid crystal display device, and a patternable overcoat, for example. In addition, by using a hole forming photomask at the time of patterning exposure to an uncured coating film, a hole can be formed and it is useful as an interlayer insulation film. In addition, at the time of exposure to an uncured coating film, a transparent film can be formed by performing only whole surface exposure, heat-hardening, or heat-hardening, without using a photomask. This transparent film is useful as an overcoat. It can also be used for display devices such as touch panels. Thereby, the display device provided with a high quality coating film or a patterned coating film can be manufactured with high yield.

Curable resin composition of this invention is a material for forming various film | membrane and a patterned coating film, for example, the transparent film which comprises a part of a color filter and / or an array substrate, a patterned coating film, a photospacer, an overcoat, an insulating film, a liquid crystal It is suitable for forming an alignment control projection, a micro lens, a coat layer and the like. In addition, a display device, such as a liquid crystal display device, an organic EL device, including a color filter, an array substrate, or the like having these coating films or a patterned coating film as part of its component parts, and also such color filters and / or array substrates, It can be used for electronic paper and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are the mass% and a mass part, unless it mentions specially.

Synthesis Example  One

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. 40 parts methacrylic acid subsequently; And a mixture of the monomer (I-1) and the monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 360 parts of diethyleneglycol methylmethyl ether 190 parts The solution dissolved in was prepared, and this solution was dripped in the flask heated to 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ethers in the flask over 5 hours using the other dropping pump. It dripped. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin A) having a solid content of 42.3%. As for the weight average molecular weight of obtained resin A, the acid value of 8000 and molecular weight distribution of 1.91, and solid content conversion was 60 mg-KOH / g, and the epoxy equivalent was 257 g / eq. Resin A has the following structural unit.

Synthesis Example  2

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to substitute a nitrogen atmosphere, and 248 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C while stirring. Subsequently, 63 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 27 parts, A mixed solution of 210 parts of methyl methacrylate and 195 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, the mixed solution which melt | dissolved 12 parts of 2,2'- azobis (2, 4- dimethylvaleronitrile) in 245 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. After the dropping was completed, the mixture was maintained 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 weight average molecular weight of obtained resin Ba was 24500, the molecular weight distribution was 2.03, and the acid value of solid content conversion was 146 mg-KOH / g, and epoxy equivalent was 2268 g / eq. Resin Ba has the following structural unit.

Synthesis Example  3

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to substitute a nitrogen atmosphere, and 256 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C while stirring. Subsequently, 81 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 27 parts, A mixed solution of 144 parts of styrene, 48 parts of methyl methacrylate and 184 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, the mixed solution which melt | dissolved 12 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 248 parts of propylene glycol monomethyl ether acetate was dripped 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 Bb) solution having a solid content of 31.0%. Obtained resin Bb had a weight average molecular weight of 21000 and a molecular weight distribution of 2.07 and an acid value of solid content of 185 mg-KOH / g and an epoxy equivalent of 1985 g / eq. Resin Bb has the following structural unit.

Synthesis Example  4

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace with a nitrogen atmosphere, and 240 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C while stirring. Subsequently, 81 parts of methacrylic acid, a mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in the mixture = 50:50} 27 parts, A mixed solution of 48 parts of styrene, 144 parts of methyl methacrylate, and 172 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, the mixed solution which melt | dissolved 8 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 280 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. After the dropping was completed, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Bc) solution having a solid content of 30.7%. As for the weight average molecular weight of obtained resin Bc, the acid value of 25730 and molecular weight distribution was 176 mg-KOH / g, epoxy equivalent 2058 g / eq. Resin Bc has the following structural units.

Synthesis Example  5

A proper amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace with a nitrogen atmosphere, and 240 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C while stirring. Then, 87 parts of methacrylic acid, the mixture of monomer (I-1) and monomer (II-1) {molar ratio of monomer (I-1): monomer (II-1) in a mixture = 50: 50} 27 parts, A mixed solution of 93 parts of styrene, 93 parts of methyl methacrylate, and 172 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, the mixed solution which melt | dissolved 8 parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 280 parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. After the dropping was completed, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin Bd) solution having a solid content of 30.9%. The acid value of 24090, molecular weight distribution 2.18, and solid content conversion of the weight average molecular weight of obtained resin Bd was 184 mg-KOH / g, and the epoxy equivalent was 1886 g / eq. Resin Bd has the following structural units.

<Measurement of molecular weight>

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of obtained resin was performed on condition of the following using GPC method.

Apparatus: K2479 [manufactured by Shimadzu Seisakusho Corporation]

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 ml / min

Detector: RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

<Measurement of epoxy equivalent>

0.2 g of the resin solution obtained above was weighed into a 50 mL stopper flask, and 5 ml of toluene and 20 ml of acetic acid were added to prepare a sample for measurement. One drop of 1% crystal violet / acetic acid solution was added to this sample for measurement as an indicator, and titrated with 0.1 N hydrogen bromide / acetic acid solution to obtain an epoxy equivalent [g / eq] according to the following formula.

B: Amount of 0.1 N hydrogen bromide / acetic acid solution consumed for titration to the end point (ml)

F: factor of 0.1 N hydrogen bromide / acetic acid solution

W: Amount of measurement sample (g) used for titration

N: solid content (%) of the resin solution obtained above

Example  1 to 4 and Comparative example  1 to 2

<Preparation of curable resin composition>

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

In addition, in Table 1, content of resin (A) shows the mass part of solid content conversion.

Resin (A); Resin synthesized in Synthesis Example 1

Resin (Ba); Resin synthesized in Synthesis Example 2

Resin (Bb); Resin synthesized in Synthesis Example 3

Resin (Bc); Resin synthesized in Synthesis Example 4

Resin (Bd); Resin synthesized in Synthesis Example 5

Polymerizable compound (C); Dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.]

Polymerization initiator (D); Da; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-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 Kagaku Co., Ltd.]

Polymerization initiation aid (D1); 2,4-diethyl thioxanthone [KAYACURE DETX-S; Nihon Kayaku Co., Ltd. product; Thioxanthone compound

Antioxidant (F); 4,4'-butane-1,1-diylbis (6-tert-butyl-m-cresol; Smithizer® BBM-S; manufactured by Sumitomo Chemical Co., Ltd.]

Surfactant (H); Ha; Polyether-modified silicone oil (Doore silicon SH8400; Doore Dow Corning Co., Ltd. product)

Solvent (E); Ea; Diethylene glycol ethyl methyl ether

Solvent (E); Eb; Propylene Glycol Monomethyl Ether Acetate

Solvent (E); Ec; 3-methoxy-1-butanol

In addition, the mass ratio of solvent (Ea)-(Ee) in a solvent (E) was made into the value shown in Table 1, and the solvent (E) was mixed so that solid content of curable resin composition might become "solid content (%)" of Table 1. .

<Measurement of transmittance of the composition>

An ultraviolet-visible near-infrared spectrophotometer [V-650; respectively about the obtained photosensitive resin composition]; The average transmittance (%) in 400-700 nm was measured using Nippon Bunco Co., Ltd. product (quartz cell, optical path length; 1 cm). The results are shown in Table 2.

<Production of Curing Film>

A square glass substrate (Eagle XG; manufactured by Corning Corporation) having one side of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. After spin-coating the photosensitive resin composition on this glass substrate so that the film thickness after postbaking may be set to 3.0 micrometers, and drying it under reduced pressure until the pressure reduction degree becomes 66 kPa with a pressure reduction dryer (made by Microtech Co., Ltd.), Prebaked at 90 degreeC with a hotplate for 80 second, and dried, and formed the composition layer. After allowing to cool, an exposure machine [TME-150RSK; Topcon Co., Ltd. light source; Ultra-high pressure mercury lamp] was used to irradiate light with an exposure dose of 60 mJ / cm 2 (365 nm standard) in an atmospheric atmosphere. In addition, irradiation to the composition layer at this time, the light emitted from an ultra-high pressure mercury lamp, the optical filter [UV-31; Asahi Bunko Co., Ltd.] was passed through. After light irradiation, the composition layer after exposure was immersed at 25 degreeC for 60 second, and immersed in the aqueous developing solution containing 0.18% of nonionic surfactant and 0.06% of potassium hydroxide, and also washed with water. Then, it heated for 15 minutes at 235 degreeC in oven, and obtained the cured film.

<Measurement of transmittance of the cured film>

The average transmittance | permeability (%) in 400-700 nm was measured for the obtained cured film using the microscopic spectrophotometer (OSP-SP200; Olympus company). The results are shown in Table 2.

<Pattern forming method>

A square glass substrate (Eagle XG; manufactured by Corning Corporation) having one side of 2 inches was washed sequentially with a neutral detergent, water, and isopropanol, and dried. On this glass substrate, the photosensitive resin composition was spin-coated, and after pressure-reducing until it became 66 Pa with a pressure reduction dryer, it prebaked at 90 degreeC with a hotplate for 80 second to form a composition layer. After allowing to cool, the interval between the substrate on which the composition layer was formed and the quartz glass photomask was set to 150 µm, and an exposure machine [TME-150RSK; Topcon Co., Ltd. light source; Ultra-high pressure mercury lamp] was used to irradiate light with an exposure dose of 60 mJ / cm 2 (365 nm standard) in an atmospheric atmosphere. In addition, irradiation to the composition layer at this time, the light emitted from an ultra-high pressure mercury lamp, the optical filter [UV-31; Asahi Bunko Co., Ltd.] was passed through. Further, as a photomask, a photomask in which a pattern (having a square light-transmitting portion having one side of 3 µm to 15 µm and having a square interval of 100 µm and formed by 5600 pieces) (that is, a light-transmitting portion) was formed on the same plane. And a halftone mask having two types of transmittances of 100% and 25%.

After light irradiation, the coating film was immersed and developed at 25 DEG C for 60 seconds in an aqueous developing solution containing 0.18% of a nonionic surfactant and 0.06% of potassium hydroxide, followed by further washing with water. Then, it post-baked at 235 degreeC for 15 minutes in oven, and obtained the resin patterned coating film.

<Adhesive evaluation>

About the obtained patterned coating film, the optical microscope [Axio Imager MAT; In the case of Carl Zeiss Co., Ltd.], when the pattern obtained from the photomask pattern remains on a board | substrate without peeling, even if one is peeled off, it described in Table 2 as x. When the pattern obtained from the smaller size photomask pattern remains, it can be judged that adhesiveness is favorable.

From the result of Table 2, it was confirmed that the patterned coating film obtained from the photocurable resin composition of this invention is excellent in adhesiveness, without reducing the transmittance | permeability of hardened | cured material.

According to this invention, the curable resin composition which can manufacture the patterned coating film excellent in adhesiveness can be provided. The obtained patterned coating film can be used suitably for a display apparatus.

Claims (6)

Curable resin composition containing following resin (A), following resin (B), a polymeric compound (C), a polymerization initiator (D), and a solvent (E).
Resin (A); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin whose epoxy equivalent is 200 g / eq or more and 500 g / eq or less.
Resin (B); It includes the structural unit derived from at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the structural unit derived from the monomer which has a C2-C4 cyclic ether structure and ethylenically unsaturated bond, And resin having an epoxy equivalent of 1200 g / eq or more and 2600 g / eq or less. Curable resin composition of Claim 1 whose content ratio of resin (A) and resin (B) is 30: 70-80: 20 on a mass basis. The curable resin composition of Claim 1 or 2 in which a polymerization initiator contains a biimidazole compound and O-acyl oxime compound. The patterned coating film formed using the curable resin composition of Claim 1 or 2. The photospacer formed using the curable resin composition of Claim 1 or 2. At least 1 sort (s) chosen from the group which consists of the patterned coating film formed using the curable resin composition of Claim 1, or the photospacer formed using the curable resin composition of Claim 1, or 2 Display device including.