KR20130050241A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curing resin composition is provided to be possible to provide the short drying time at the vacuum drying. CONSTITUTION: A curable resin composition includes the curable resin and the solvent. The solvent comprises dialkyleneglycol dialkyl ether, a solvent-E1, and a solvent-E2 mentioned below. The content of the dialkyleneglycol dialkyl ether is over than 1 mass% and less than 45 mass% about the total amount of the solvent. The solvent-E1 is different with the dialkyleneglycol dialkyl ether and has the evaporation rate of over than 40 and less than 100 about the evaporation rate of 100 for the butyl acetate. The solvent-E2 is different with the dialkyleneglycol dialkyl ether and has the evaporation rate of over than 13 and less than 40 about the evaporation rate of 100 for the butyl acetate. The cured film is formed from the curable resin composition. The display device includes the cured film.

Description

CURABLE RESIN COMPOSITION [0001]

The present invention relates to a curable resin composition.

In recent liquid crystal display devices, in order to form cured films, such as a photo spacer and an overcoat, curable resin composition is used. As such a curable resin composition, a composition containing diethylene glycol ethyl methyl ether, 3-methoxy-1-butanol and propylene glycol monomethyl ether as a solvent is known (JP2010-152335-A).

In the conventionally proposed curable resin composition, after apply | coating this curable resin composition to a board | substrate, the drying time at the time of drying under reduced pressure may be long, and it may not always be satisfied satisfactorily.

The present invention includes the following inventions.

[1] containing a resin having a curability and a solvent,

The solvent contains a dialkylene glycol dialkyl ether, the following solvent (E1), and the following solvent (E2),

Curable resin composition whose content of dialkylene glycol dialkyl ether is 1 mass% or more and 45 mass% or less with respect to the total amount of a solvent.

Solvent (E1): A solvent that is different from the dialkylene glycol dialkyl ether and the evaporation rate is 40 or more and 100 or less when the evaporation rate is 100 as the evaporation rate of butyl acetate.

Solvent (E2): A solvent that is different from the dialkylene glycol dialkyl ether and the evaporation rate is from 13 to less than 40 when the evaporation rate is 100 to the evaporation rate of butyl acetate.

[2] The curable resin has a structural unit derived from at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. Curable resin composition as described in [1] which is a copolymer containing the structural unit derived from a monomer.

[3] Curable resin composition as described in [1] or [2] which further contains antioxidant.

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

[5] A display device comprising the cured film described in [4].

(6) (1) Process of apply | coating curable resin composition in any one of [1]-[3] to a board | substrate, (2) Process of drying the apply | coated curable resin composition under reduced pressure, and forming a composition layer, (( 3) The manufacturing method of the cured film containing the process of heating a composition layer.

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

In this specification, the compound illustrated as each component can be used individually or in combination of 2 types, unless a special understanding is requested | required.

Curable resin composition of this invention contains resin which has curability (henceforth "resin (A)"), and a solvent (E),

The solvent (E) contains a dialkylene glycol dialkyl ether, the following solvent (E1), and the following solvent (E2),

It is curable resin composition whose content of dialkylene glycol dialkyl ether is 1 mass% or more and 45 mass% or less with respect to the total amount of a solvent.

Solvent (E1): The solvent which is different from dialkylene glycol dialkyl ether and is 40 or more and 100 or less when evaporation rate makes evaporation rate of butyl acetate 100.

Solvent (E2): A solvent which is different from dialkylene glycol dialkyl ether and is 13 or more and less than 40 when the evaporation rate is 100, the evaporation rate of butyl acetate.

Furthermore, the curable resin composition of this invention has a compound (following) which has 1 or more types of groups (henceforth a "(meth) acryloyl group") chosen from the group which consists of acryloyl group and methacryloyl group. It is preferable to contain 1 or more types of components chosen from the group which consists of "(meth) acryl compound (B)", antioxidant (F), and surfactant (H).

In addition, the curable resin composition of this invention may be called 1 or more types of epoxy resin (henceforth "epoxy resin (C)") chosen from the group which consists of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin. ), At least one compound selected from the group consisting of a polymerization initiator (D), a polymerization initiator (D1), a thiol compound (T), a polyvalent carboxylic anhydride and a polyvalent carboxylic acid (hereinafter referred to as "polyvalent carboxylic acid (G) ) "And an imidazole compound (J), and 1 or more types of components chosen from the group which consists of these may be included.

<Resin (A)>

Resin (A) is resin which has curability, thermosetting resin is preferable, resin which hardens by 60 degreeC or more heat is more preferable, and 1 or more types chosen from the group which consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (following) Derived from a structural unit derived from "(a)", and a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter may be referred to as "(b)"). More preferred are copolymers containing structural units. This copolymer may further have a structural unit copolymerizable with (a) and originating in the monomer (Hereinafter, it may be called "(c)") which does not have a C2-C4 cyclic ether structure.

Resin (A), Preferably it is the following resin [K1] and resin [K2].

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

Resin [K2]: A copolymer of (a), (b) and (c).

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic 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, 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- N, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [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 monophthalate [2- (meth) acryloyloxyethyl] ] Esters;

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

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

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

(b) means the polymerizable compound which has a C2-C4 cyclic ether structure (for example, 1 or more types chosen from the group which consists of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenically unsaturated bond. 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 a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which linear or branched unsaturated aliphatic hydrocarbons are epoxidized, and unsaturated alicyclic hydrocarbons are epoxidized. And monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure that is used.

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.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE 2000; manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) Acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Chemical Co., Ltd.), formula (I The compound represented by) and the compound represented by Formula (II), etc. are mentioned.

[In 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 a C1-C6 alkanediyl group.

* 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.

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-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 hydrogen atoms, methyl groups, hydroxymethyl groups, 1-hydroxyethyl groups and 2-hydroxyethyl groups, and more preferably hydrogen atoms and methyl groups.

Examples of the alkanediyl group are 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-1, 6-diyl group etc. are mentioned.

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 and * -CH. ₂ CH ₂ -O- may be mentioned. * Represents the number of bonds with O.

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) may each be used alone, or may be mixed and used at any ratio. When used by mixing, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: on a molar basis. 10, More preferably, it is 20: 80-80: 20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable.

Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 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 preferable. As (b3), tetrahydrofurfuryl acrylate (For example, biscoat V # 150, the Osaka Yuki Chemical Co., Ltd. product), tetrahydrofurfuryl methacrylate, etc. are mentioned.

As (b), it is preferable that it is (b1) from the point which can make higher reliability, such as heat resistance and chemical-resistance, of a 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 known as "dicyclopentanyl (meth) acrylate". , May be referred to as "tricyclodecyl (meth) acrylate.", Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclophene" It is called "tenyl (meth) acrylate"), dish Lofentanyloxyethyl (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 itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate 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. .

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

structural unit derived from (a); 5 ~ 60 mol%

structural unit derived from (b); 40-95 mol% is preferable,

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); 50-90 mol% is more preferable.

When the ratio of the structural unit which comprises resin [K1] exists in the said range, it exists in the tendency which is excellent in the storage stability of curable resin composition, the chemical-resistance, heat resistance, and mechanical strength of the cured film obtained.

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (Okasu Takayuki, published by Japan Chemical Co., Ltd., First Edition, March 1, 1972). It can manufacture by reference.

Specifically, the method of heating and keeping warm while stirring in a deoxygen atmosphere by putting predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen, for example is mentioned. . In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. As a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide etc.) are mentioned, for example. As a solvent, what is necessary is just to melt | dissolve each monomer, and the solvent etc. which are mentioned later used for curable resin composition are mentioned.

In addition, the obtained resin may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. Since the solution after reaction can be used as it is for manufacture of curable resin composition by using the solvent used for curable resin composition of this invention especially as a polymerization solvent, the manufacturing process of curable resin composition can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the whole structural unit which comprises resin [K2],

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

structural unit derived from (b); 2 ~ 95 mol%

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

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

structural unit derived from (b); 5 to 80 mol%

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

Moreover, as for the total amount of the structural unit derived from (a), and the structural unit derived from (b), 70-99 mol% is preferable with respect to the total mole number of all the structural units which comprise resin [K2], and 90-99 Mole% is more preferable.

When the ratio of the structural unit of resin [K2] is in the above-mentioned range, there exists a tendency which is excellent in the storage stability of curable resin composition, the chemical-resistance, heat resistance, and mechanical strength of the cured film obtained.

Resin [K2] can be manufactured by the method similar to resin [K1].

As a specific example of resin [K1], the compound represented by (meth) acrylic acid / formula (I-1) may be abbreviated as "formula (I-1)" hereafter. The same.), The copolymer of (meth) acrylic acid / formula (I-2), the copolymer of (meth) acrylic acid / formula (I-3), the air of (meth) acrylic acid / formula (I-4) Copolymer, copolymer of (meth) acrylic acid / formula (I-5), copolymer of (meth) acrylic acid / formula (I-6), copolymer of (meth) acrylic acid / formula (I-7), (meth) Copolymer of acrylic acid / formula (I-8), copolymer of (meth) acrylic acid / formula (I-9), copolymer of (meth) acrylic acid / formula (I-10), (meth) acrylic acid / formula (I -11) copolymer, (meth) acrylic acid / copolymer of formula (I-12), (meth) acrylic acid / copolymer of formula (I-13), (meth) acrylic acid / air of formula (I-14) Copolymer, copolymer of (meth) acrylic acid / formula (I-15), copolymer of (meth) acrylic acid / formula (II-1), copolymer of (meth) acrylic acid / formula (II-2), (meth) Copolymer of methacrylic acid / formula (II-3), copolymer of (meth) acrylic acid / formula (II-4), copolymer of (meth) acrylic acid / formula (II-5), (meth) acrylic acid / formula ( II-6) copolymer, (meth) acrylic acid / copolymer of formula (II-7), (meth) acrylic acid / copolymer of formula (II-8), (meth) acrylic acid / formula (II-9) Copolymer, copolymer of (meth) acrylic acid / formula (II-10), copolymer of (meth) acrylic acid / formula (II-11), copolymer of (meth) acrylic acid / formula (II-12), (meth Copolymer of acrylic acid / formula (II-13), copolymer of (meth) acrylic acid / formula (II-14), copolymer of (meth) acrylic acid / formula (II-15), (meth) acrylic acid / formula ( I-1) / copolymer of formula (II-1), (meth) acrylic acid / copolymer of formula (I-2) / formula (II-2), (meth) acrylic acid / formula (I-3) / formula Copolymer of (II-3), copolymer of (meth) acrylic acid / formula (I-4) / formula (II-4), of (meth) acrylic acid / formula (I-5) / formula (II-5) Copolymer, (meth) acrylic acid / copolymer of formula (I-6) / formula (II-6), (meth) a Copolymer of lactic 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) / formula (II-10), (meth) acrylic acid / formula (I-11) / formula (II -11) copolymer, (meth) acrylic acid / copolymer of formula (I-12) / formula (II-12), (meth) acrylic acid / copolymer of formula (I-13) / formula (II-13) , (Meth) acrylic acid / copolymer of formula (I-14) / formula (II-14), (meth) acrylic acid / copolymer of formula (I-15) / formula (II-15), (meth) acrylic acid / Copolymer of formula (I-1) / formula (I-7), copolymer of (meth) acrylic acid / formula (I-1) / formula (II-7), air of crotonic acid / formula (I-1) Copolymer, copolymer of crotonic acid / formula (I-2), copolymer of crotonic acid / formula (I-3), copolymer of crotonic acid / formula (I-4), crotonic acid / formula (I-5) Copolymer of crotonic acid / formula (I-6), copolymer of crotonic acid / formula (I-7), copolymer of crotonic acid / formula (I-8), crotonic acid / formula (I-) 9), public Copolymer, copolymer of crotonic acid / formula (I-10), copolymer of crotonic acid / formula (I-11), copolymer of crotonic acid / formula (I-12), crotonic acid / formula (I-13) Copolymer of, crotonic acid / copolymer of formula (I-14), copolymer of crotonic acid / formula (I-15), copolymer of crotonic acid / formula (II-1), crotonic acid / formula (II- Copolymer of 2), copolymer of crotonic acid / formula (II-3), copolymer of crotonic acid / formula (II-4), copolymer of crotonic acid / formula (II-5), crotonic acid / formula ( II-6) copolymer, crotonic acid / copolymer of formula (II-7), crotonic acid / copolymer of formula (II-8), crotonic acid / copolymer of formula (II-9), crotonic acid / Copolymer of formula (II-10), copolymer of crotonic acid / formula (II-11), copolymer of crotonic acid / formula (II-12), copolymer of crotonic acid / formula (II-13), croton Copolymer of acid / formula (II-14), copolymer of crotonic acid / formula (II-15), copolymer of maleic acid / formula (I-1), copolymer of maleic acid / formula (I-2) , Copolymer of maleic acid / formula (I-3), maleic acid / formula Copolymer of (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), maleic acid / copolymer of formula (I-14), maleic acid / air of formula (I-15) Copolymer, maleic acid / copolymer of formula (II-1), maleic acid / copolymer of formula (II-2), maleic acid / copolymer of formula (II-3), maleic acid / formula (II-4) Copolymer of maleic acid / formula (II-5), copolymer of maleic acid / formula (II-6), copolymer of maleic acid / formula (II-7), maleic acid / formula (II- 8), maleic acid / copolymer of formula (II-9), maleic acid / copolymer of formula (II-10), maleic acid / copolymer of formula (II-11), maleic acid / formula ( II-12) copolymer, maleic acid / copolymer of formula (II-13), maleic acid / copolymer of formula (II-14), maleic acid / formula (II-15) Polymer, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-2), (meth) acrylic acid / maleic anhydride / formula Copolymer of (I-3), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-4), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-5), (meth) Copolymer of acrylic acid / maleic anhydride / formula (I-6), copolymer of (meth) acrylic acid / maleic anhydride / formula (I-7), (meth) acrylic acid / maleic anhydride / formula (I-8) Copolymer of (meth) acrylic acid / maleic anhydride / formula (I-9), copolymer of (meth) acrylic acid / maleic anhydride / 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 / copolymer of formula (I-14), (meth) acrylic acid / maleic acid Copolymer of anhydride / formula (I-15), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-2), (Meth) acrylic acid / maleic anhydride / copolymer of formula (II-3), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-4), (meth) acrylic acid / maleic anhydride / formula (II -5) copolymer, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-6), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-7), (meth) acrylic acid / Copolymer of maleic anhydride / formula (II-8), copolymer of (meth) acrylic acid / maleic anhydride / formula (II-9), air of (meth) acrylic acid / maleic anhydride / formula (II-10) Copolymer, 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 / formula Copolymer of (II-13), (meth) acrylic acid / maleic anhydride / copolymer of formula (II-14) There may be mentioned copolymers of (meth) acrylic acid / maleic anhydride / copolymer of formula (II-15) or the like.

As a specific example of resin [K2], the copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate, and the air of (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) acrylic acid / Copolymer of formula (I-5) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of 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, Ball of (meth) acrylic acid / formula (I-12) / methyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-13) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-14) / methyl (meth) acrylate, (meth) acrylic acid / Copolymer of formula (I-15) / methyl (meth) acrylate, (meth) acrylic acid / copolymer of formula (II-1) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-2 Copolymer of () / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-3) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-4) / methyl (meth) Copolymer of acrylate, copolymer of (meth) acrylic acid / formula (II-5) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-6) / methyl (meth) acrylate, Copolymer of (meth) acrylic acid / formula (II-7) / methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-8) / methyl (meth) acrylate, (meth) acrylic acid / formula Copolymer of (II-9) / methyl (meth) acrylate, (meth A copolymer of acrylic acid / formula (II-10) / methyl (meth) acrylate, a copolymer of (meth) acrylic acid / formula (II-11) / methyl (meth) acrylate, (meth) acrylic acid / formula (II -12) / copolymer of methyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-13) / methyl (meth) acrylate, (meth) acrylic acid / formula (II-14) / methyl ( Copolymer of meth) acrylate, copolymer of (meth) acrylic acid / formula (II-15) / methyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymer of (meth) acrylic acid / formula (II-1) / dicyclopentanyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / dicyclopentanyl Copolymer of (meth) acrylate, copolymer of crotonic acid / formula (I-1) / dicyclopentanyl (meth) acrylate, of maleic acid / formula (I-1) / dicyclopentanyl (meth) acrylate Copolymer, (meth) acrylic acid / maleic acid free Copolymer of water / 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 A 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, copolymer of (meth) acrylic acid / formula (I-1) / phenyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / phenyl (meth) acrylate, ( Copolymer of methacrylic acid / formula (I-1) / formula (II-1) / phenyl (meth) acrylate, copolymer of crotonic acid / formula (I-1) / phenyl (meth) acrylate, maleic acid / Formula (I-1) / phenyl (meth) arc Copolymer of rate, (meth) acrylic acid / maleic anhydride / copolymer of formula (I-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / Copolymer of phenyl (meth) acrylate, copolymer of crotonic acid / formula (II-1) / phenyl (meth) acrylate, copolymer of maleic acid / formula (II-1) / phenyl (meth) acrylate, Copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / phenyl (meth) acrylate, (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / phenyl (meth) acrylic Copolymer of the rate, the copolymer of (meth) acrylic acid / formula (I-1) / diethyl maleate, the copolymer of (meth) acrylic acid / formula (II-1) / diethyl maleate, (meth) acrylic acid / formula ( Copolymer of I-1) / formula (II-1) / diethyl maleate, copolymer of crotonic acid / formula (I-1) / diethyl maleate, maleic acid / formula (I-1) / diethyl maleate Copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / maleic acid Copolymer of methyl, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / diethyl maleate, copolymer of crotonic acid / formula (II-1) / diethyl maleate, maleic acid / Copolymer of formula (II-1) / diethyl maleate, (meth) acrylic acid / maleic anhydride / copolymer of formula (II-1) / diethyl maleate, (meth) acrylic acid / formula (II-1) / Copolymer of methyl (meth) acrylate / diethyl maleate, copolymer of (meth) acrylic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / formula (II-1 ) / Copolymer of 2-hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / 2-hydroxyethyl (meth) acrylate, croton Copolymer of acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, copolymer of maleic acid / formula (I-1) / 2-hydroxyethyl (meth) acrylate, (meth) Acrylic acid / maleic anhydride / formula of formula (I-1) / 2-hydroxyethyl (meth) acrylate Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, crotonic acid / formula (II-1) / 2-hydroxyethyl Copolymer of (meth) acrylate, maleic acid / formula (II-1) / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / formula (II-1) / 2 -Copolymer of hydroxyethyl (meth) acrylate, copolymer of (meth) acrylic acid / formula (II-1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid Copolymer of / formula (I-1) / bicyclo [2.2.1] hept-2-ene, air of (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] copolymer of hept-ene, maleic acid / formula (I-1) / bicyclo [2.2.1] hept-2-ene copolymer, (meth) acrylic acid / maleic anhydride / formula (I- One)/ Copolymer of cyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / bicyclo [2.2.1] hept-2-ene, Copolymer of crotonic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene, air of maleic acid / formula (II-1) / bicyclo [2.2.1] hept-2-ene Copolymer, 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) Copolymer of acrylate / bicyclo [2.2.1] hept-2-ene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide, (meth) acrylic acid / formula (II- 1) copolymer of / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide, crotonic acid / formula (I-1) ) / N-cyclohexylmaleimide copolymer, maleic acid / formula (I-1) / N-cyclohexylmaleimide copolymer, (meth) acrylic acid / maleic anhydride / formula (I-1) / N- Cyclohexylmaleimide Copolymer, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide, air of crotonic acid / formula (II-1) / N-cyclohexylmaleimide Copolymer, copolymer of maleic acid / formula (II-1) / N-cyclohexylmaleimide, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexylmaleimide, (meth A copolymer of acrylic acid / formula (II-1) / methyl (meth) acrylate / N-cyclohexyl maleimide, a copolymer of (meth) acrylic acid / formula (I-1) / styrene, (meth) acrylic acid / formula Copolymer of (II-1) / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / styrene, copolymer of crotonic acid / formula (I-1) / styrene, Copolymer of maleic acid / formula (I-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / styrene, (meth) acrylic acid / formula (I-1) / methyl ( Copolymer of meth) acrylate / styrene, copolymer of crotonic acid / formula (II-1) / styrene, Copolymer of acid / formula (II-1) / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (II-1) / styrene, (meth) acrylic acid / formula (II-1) / methyl (meth) Copolymer of acrylate / styrene, copolymer of (meth) acrylic acid / formula (I-1) / N-cyclohexylmaleimide / styrene, (meth) acrylic acid / formula (II-1) / N-cyclohexylmalee Copolymer of mid / styrene, copolymer of (meth) acrylic acid / formula (I-1) / formula (II-1) / N-cyclohexylmaleimide / styrene, crotonic acid / formula (I-1) / N- Copolymer of cyclohexylmaleimide / styrene, maleic acid / formula (I-1) / N-cyclohexyl maleimide / styrene, copolymer of (meth) acrylic acid / maleic anhydride / formula (I-1) / N- Copolymer of cyclohexylmaleimide / styrene, copolymer of (meth) acrylic acid / formula (I-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene, crotonic acid / formula (II-1) Copolymer of / N-cyclohexylmaleimide / styrene, maleic acid / formula (II- 1) / N-cyclohexylmaleimide / styrene copolymer, (meth) acrylic acid / maleic anhydride / formula (II-1) / N-cyclohexyl maleimide / styrene copolymer, (meth) acrylic acid / formula ( And copolymers of II-1) / methyl (meth) acrylate / N-cyclohexylmaleimide / styrene.

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, particularly preferably 50 It is more than mg-KOH / g 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 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.

Content of resin (A) is 30-90 mass% with respect to solid content of curable resin composition of this invention, More preferably, it is 35-80 mass%, More preferably, it is 40-70 mass%. When content of resin (A) exists in the said range, the cured film obtained tends to be excellent in heat resistance and excellent in adhesiveness with a board | substrate, and chemical-resistance. Here, solid content of curable resin composition means the quantity which limited content of a solvent (E) by the total amount of curable resin composition of this invention.

<(Meth) acrylic compound (B)>

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

As a (meth) acryl compound (B) which has one (meth) acryloyl group, the same thing as the compound mentioned as said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is desirable.

As a (meth) acryl compound which has two (meth) acryloyl groups, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, and 1, 6- hexanediol di (meth) acryl 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 neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (Meth) acrylate, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Examples of the (meth) acryl compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tree ( Meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritolhepta (meth) acrylate, tri Pentaerythritol octa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate with an acid anhydride, Reactant of dipentaerythritol penta (meth) acrylate with acid anhydride, reactant of tripentaerythritolhepta (meth) acrylate with acid anhydride, caprolactone modified trimethylolpropanetri (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 dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, caprolactone modified tripentaerythritol hexa (Meth) acrylate, caprolactone modified tripentaeryeri Hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, reactant caprolactone modified dipentaerythritol penta (meth) acrylate And a reactant with an acid anhydride, a reactant with a caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride, and the like.

As a (meth) acryl compound (B), the (meth) acryl compound which has three or more (meth) acryloyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

When curable resin composition of this invention contains a (meth) acryl compound (B), the content becomes like this. Preferably it is 20-100 mass parts with respect to 100 mass parts of content of resin (A), More preferably, it is 25-70 It is a mass part. When content of a (meth) acryl compound (B) exists in the said range, there exists a tendency for the chemical-resistance and mechanical strength of the cured film obtained to become favorable.

<Epoxy Resin (C)>

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

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure, and can be synthesized by reacting epichlorohydrin with phenols, polyhydric alcohols, and the like.

Examples of the glycidyl ether type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, o-cresol novolak type epoxy resins, and trishydroxyphenylmethane type epoxy resins. Resin can be mentioned.

A glycidyl ester type epoxy resin is an epoxy resin which has a glycidyl ester structure, and is synthesize | combined by making carbonyl groups, such as a phthalic acid derivative and a fatty acid, react with epichlorohydrin.

Examples of the glycidyl ester type epoxy resins include glycidyl ester type epoxy resins derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, and terephthalic acid.

The epoxy resin (C) used for the curable resin composition of this invention is a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, o-cresol novolak-type epoxy resin, a polyphenol type epoxy resin, etc. It is preferable that it is a glycidyl ether type epoxy resin. Especially, bisphenol-A epoxy resin is especially preferable.

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

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

The acid value of an epoxy resin (C) is normally less than 30 mg-KOH / g, and it is preferable that it is 10 mg-KOH / g or less.

Moreover, the weight average molecular weight of an epoxy resin (C) becomes like this. Preferably it is 300-10,000, More preferably, it is 400-6,000, More preferably, it is 500-4,800.

When curable resin composition of this invention contains an epoxy resin (C), the content becomes like this. Preferably it is 1-60 mass parts with respect to 100 mass parts of total content of resin (A) and a (meth) acryl compound (B). More preferably, it is 5-50 mass parts. When content of an epoxy resin (C) exists in the said range, the cured film obtained tends to be excellent in adhesiveness with a board | substrate.

<Polymerization Initiator (D)>

As the polymerization initiator (D), any compound capable of generating an active radical, an acid or the like by the action of light or heat to initiate polymerization can be used without any particular limitation.

As a polymerization initiator (D), the polymerization initiator containing 1 or more types chosen from the group which consists of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound is preferable, and O- The polymerization initiator containing an acyl oxime compound is more preferable. If it is these polymerization initiators, it exists in the high sensitivity and there exists a tendency for the transmittance | permeability in a visible light region to become high.

The O-acyl oxime compound is a compound having a partial structure represented by 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-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine. You may use commercial items, such as IRGACURE (trademark) OXE01, OXE02 (above BASF Corporation make), and N-1919 (ADEKA Corporation make).

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 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 -On. 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 Unexamined-Japanese-Patent No. 2002-544205.

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxy Oligomers of hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, (alpha)-diethoxy acetophenone and benzyl dimethyl ketal are mentioned.

In terms of sensitivity, as the alkylphenone compound, a compound having a partial structure represented by 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 (trichloro Rhomethyl) -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 and 2,4-bis (trichloromethyl)- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine is mentioned.

2,4,6-trimethyl benzoyl diphenyl phosphine oxide etc. are mentioned as an acyl phosphine oxide compound. You may use commercial items, such as IRGACURE 819 (made by Chiba Japan 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.), imidazole in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group A compound (for example, see JPH07-10913-A etc.) is mentioned.

Moreover, as a polymerization initiator (D), benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether: benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzo Benzophenones such as phenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone compound; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. It is preferable to use these in combination with the polymerization start adjuvant (D1) (especially amines) mentioned later.

An acid generator can also be used as a polymerization initiator (D).

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, di Onium salts, such as phenyl iodonium hexafluoro antimonate, nitrobenzyl tosylate, and benzoin tosylate are mentioned.

When curable resin composition of this invention contains a polymerization initiator (D), 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 (meth) acryl compound (B). More preferably, it is 0.5-15 mass parts, More preferably, it is 1-8 mass%. 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 pattern obtained to be high.

<Polymerization start preparation (D1)>

The polymerization initiation assistant (D1) is used together with the polymerization initiator (D) and used to promote the polymerization of the polymerizable compound (eg, (meth) acrylic compound (B)) in which polymerization is initiated by the polymerization initiator (D). Compound or sensitizer.

As a polymerization start adjuvant (D1), a thiazolin compound, an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

As a thiazolin compound, the compound represented by Formula (III-1)-Formula (III-3), the compound of JP2008-65319-A, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic 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 commercial items, such as EAB-F (made by Hodogaya Chemical 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-propoxythioke Santon etc. can be mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

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 with respect to 100 mass parts of total content of resin (A) and a (meth) acryl compound (B). Part, More preferably, it is 0.2-10 mass parts. When the amount of the polymerization start aid (D1) is within the above-described range, there is a tendency to become more sensitive when forming a pattern.

<Thiol compound (T)>

Thiol compound (T) is a compound which has a sulfanyl group (-SH) in a molecule | numerator. Especially, the compound which has two or more sulfanyl groups is preferable, and the compound which has two or more sulfanyl groups couple | bonded with the carbon atom of an aliphatic hydrocarbon structure is more preferable. It is preferable to use a thiol compound (T) with a polymerization initiator (D).

Examples of the thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate), butanediolbis (3-sulfanyl acetate), and ethylene. Glycolbis (3-Sulfanyl Acetate), Trimethylol Propane Tris (3-Sulfanyl Acetate), Butanediol Bis (3-Sulfanyl Propionate), Trimethylol Propane Tris (3-Sulfanyl Propionate), Trimethylol Propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3-sulfanylpropionate) And pentaerythritol tetrakis (3-sulfanylbutylate) and 1,4-bis (3-sulfanylbutyloxy) butane.

When curable resin composition of this invention contains a thiol compound (T), the content becomes like this. Preferably it is 10-90 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 15-70 mass parts to be. When content of a thiol compound (T) exists in the said range, there exists a tendency for a sensitivity to become high and developability becomes favorable.

<Antioxidant (F)>

As antioxidant (F), a phenolic antioxidant, sulfur type | system | group antioxidant, phosphorus antioxidant, and amine antioxidant are mentioned. Especially, since the coloring of a cured film is few, a phenolic antioxidant is preferable.

Examples of the phenolic antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and 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-methyl Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'- Thiobis (6-tert-butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a "-(mesitylene-2 , 4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert -Butyl-4-methylphenol and 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) prop At] may be mentioned -2,4,8,10--tert- butyl dibenz [d, f] [1,3,2] dioxa force pepin.

As said phenolic antioxidant, you may use a commercial item. Commercially available phenolic antioxidants include, for example, Sumilizer (registered trademark) BHT, GM, GS, GP (above, manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1076, 1330, 3114 (above, All manufactured by BASF Corporation).

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate and pentaerythritol Tetrakis (3-laurylthiopropionate). You may use a commercial item as said sulfur type antioxidant. 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 and tetra (tridecyl) -1,1,3- Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. You may use a commercial item as said phosphorus antioxidant. Commercially available phosphorus antioxidants include, for example, IRGAFOS® 168, 12, 38 (all manufactured by BASF Corporation), Adeka Stub 329K and Adeka Stub PEP36 (all manufactured by ADEKA).

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

When curable resin composition of this invention contains antioxidant (F), the content is 0.1 mass part or more and 5 mass parts or less with respect to 100 mass parts of total content of resin (A) and a (meth) acryl compound (B). Is preferable, and 0.5 mass part or more and 3 mass parts or less are more preferable. When content of antioxidant (F) exists in the said range, the cured film obtained tends to be excellent in heat resistance and pencil hardness.

<Surfactant (H)>

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

As silicone type surfactant, surfactant which has a siloxane bond is mentioned.

Specifically, Toray Silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (brand name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momental Performance Materials Japan Corporation) Company production).

As a fluorine-type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned.

Specifically, Florinate FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Park (registered trademark) F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper F552, Copper F553, copper F554, copper F555, copper F556, copper F558, copper F559, copper R30 (manufactured by DIC Corporation), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 SEI CORPORATION), Saffron (registered trademark) S381, S382, SSC101, SSC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemicals Co., Ltd.), and the like. have.

As silicone type surfactant which has a fluorine atom, surfactant which has a siloxane bond and a fluorocarbon chain | strand is mentioned. Specifically, Mega Park (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation), and the like. Preferably, Mega Park (trademark) F475 is mentioned.

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, Preferably it is 0.002 mass% or more and 0.1 mass% Hereinafter, More preferably, they are 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.

<Polyhydric carboxylic acid (G)>

Polyhydric carboxylic acid (G) is 1 or more types of compounds chosen from the group which consists of polyhydric carboxylic anhydride and polyhydric carboxylic acid. Polyhydric carboxylic acid is a compound which has two or more carboxyl groups, and polyhydric carboxylic anhydride is anhydride of polyhydric carboxylic acid. It is preferable that it is molecular weight 3000 or less, and, as for polyhydric carboxylic acid (G), it is more preferable that it is 1000 or less.

As said polyhydric carboxylic anhydride, for example, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecyl succinic anhydride, 2- (2-octa-3-enyl) succinic anhydride Linear polyhydric carboxylic acid anhydrides such as 2- (2,4,6-trimethylnona-3-enyl) amber acid anhydride, tricarvallylic anhydride and 1,2,3,4-butanetetracarboxylic dianhydride;

3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicar Acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] Such as hepta-5-ene-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hepta-5-ene-2,3-dicarboxylic acid anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyhydric carboxylic anhydride;

Phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3'4,4'-diphenylsulfontetracarboxylic acid Dianhydrides, ethylene glycol bis (anhydrotrimellitate), glycerin tris (anhydrotrimelitate), glycerin bis (anhydrotrimelitate) monoacetate, 1,3,3a, 4,5,9b-hexahydro And aromatic polyhydric carboxylic acid anhydrides such as -5- (tetrahydro-2,5-dioxo-3-furanyl) naphth [1,2-c] furan-1,3-dione.

Adeka Hardener EH-700 (brand name (the same), ADEKA Corporation), Rikacid-HH, Copper-TH, Copper-MH, Copper MH-700 (manufactured by Shin-Nihon Rika Co., Ltd.), Epikinia 126, You may use commercial items, such as YH-306 and DX-126 (manufactured by Yuca Shell Epoxy Co., Ltd.).

As said polyhydric carboxylic acid, Chain polyhydric carboxylic acid, such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, polyhydric carboxylic acid which induces a linear polyhydric carboxylic anhydride;

Alicyclic polyhydric carboxylic acids such as cyclohexanedicarboxylic acid and polyhydric carboxylic acid inducing alicyclic polyhydric carboxylic anhydride;

And aromatic polyhydric carboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, and polyhydric carboxylic acid for inducing aromatic polyhydric carboxylic anhydride.

Especially, since it is excellent in the heat resistance of a cured film, and especially transparency in a visible light range is hard to fall, chain carboxylic anhydride and an alicyclic polyhydric carboxylic anhydride are preferable, and an alicyclic polyhydric carboxylic anhydride is more preferable. Do.

When curable resin composition of this invention contains polyhydric carboxylic acid (G), the content becomes like this. Preferably it is 1-30 with respect to 100 mass parts of total content of resin (A) and a (meth) acryl compound (B). A mass part, More preferably, it is 2-20 mass parts, More preferably, it is 2-15 mass parts. When content of polyhydric carboxylic acid (G) exists in the said range, it is excellent in the heat resistance and adhesiveness of a cured film.

<Imidazole Compound (J)>

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

[In formula (2), R <^11> represents a C1-C20 alkyl group, a phenyl group, a benzyl group, or a C2-C5 cyanoalkyl group.

R ¹² to R ¹⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group or an acyl group having 1 to 20 carbon atoms, and the hydrogen atoms contained in the alkyl group and the phenyl group are substituted with hydroxy groups. It may be.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, heptadecyl group and undecyl group Can be.

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

As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristyl group and stearoyl group. .

As imidazole compound (J), for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl- 4-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methyl Imidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl-2-methyl Midazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyano Methyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole. . Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

When curable resin composition of this invention contains an imidazole compound (J), the content becomes like this. Preferably it is 0.1 mass part or more with respect to 100 mass parts of total content of resin (A) and a (meth) acryl compound (B). It is 25 mass parts or less, More preferably, it is 0.2 mass part or more and 15 mass parts or less, More preferably, it is 0.5 mass part or more and 5 mass parts or less. When content of an imidazole compound (J) exists in the said range, the cured film obtained tends to be excellent in transparency in visible region.

&Lt; Solvent (E) >

Solvent (E) contains dialkylene glycol dialkyl ether, the following solvent (E1), and the following solvent (E2).

Dialkylene glycol dialkyl ether is a solvent which consists of a compound represented by Formula (E ').

In formula (E '), R ^e1 represents a C1-C3 alkanediyl group.

R ^e2 and R ^e3 each independently represent an alkyl group having 1 to 4 carbon atoms.]

^Examples of the alkanediyl group of R ^e1 include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, and the like, and preferably an ethylene group or a propane-1,2-diyl group to be.

^Examples of the alkyl group of R ^e2 and R ^e3 include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and the like, and preferably methyl and ethyl groups.

As a dialkylene glycol dialkyl ether, Diethylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether;

Dipropylene glycol dialkyl ether, such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether, etc. are mentioned.

Among them, diethylene glycol dialkyl ether is preferably diethylene glycol dialkyl ether, more preferably diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether, and even more preferably diethylene glycol ethyl methyl ether.

The solvent (E1) is different from the dialkylene glycol dialkyl ether, and when the evaporation rate is 100, the solvent is 40 or more and 100 or less. The evaporation rate of the solvent (E1) becomes like this. Preferably it is 45 or more and less than 80, More preferably, it is 50 or more and less than 75.

In this specification, an evaporation rate means the evaporation rate of the solvent vaporized from a unit area in unit time, and evaporation rate is with respect to the evaporation rate 100 of n-butyl acetate in the temperature of 23 degreeC, and 50% of a relative humidity. It is shown by the ratio of the evaporation rate of a sample (solvent). The specific measuring method is chemical balance and filter paper No. 6 in the hood which could supply nitrogen gas. Two 70 mmφ chalets with 2 (70 mmφ) were installed, each containing 1.0 g of n-butyl acetate and 1.0 g of sample on the other, and nitrogen gas was supplied into the hood at a flow rate of 30 NL / ml. It is a method of simultaneously measuring the weight of n-butyl and a sample every 60 second, and let the average value of the evaporation rate computed from the weight after 60 second, 120 second, and 180 second pass as the evaporation rate of a sample.

Examples of the solvent (E1) include ether solvents such as ethylene glycol monomethyl ether (evaporation rate: 47), propylene glycol monomethyl ether (evaporation rate: 62), and propylene glycol monoethyl ether (evaporation rate: 46);

Ester solvents such as methyl pyruvate (evaporation rate: 42) and butyl propionate (evaporation rate: 45);

Ketone solvents such as 2-heptanone (evaporation rate: 40);

Aromatic hydrocarbon solvents such as xylene (evaporation rate: 70);

Alcohol solvents, such as 1-butanol (evaporation rate: 47), 2-butanol (evaporation rate: 89), and isobutanol (evaporation rate: 74), etc. are mentioned.

Especially, propylene glycol monomethyl ether and ethylene glycol monomethyl ether are preferable, and, as for solvent (E1), propylene glycol monomethyl ether is more preferable.

A solvent (E2) is different from dialkylene glycol dialkyl ether, and is a solvent which is 13 or more and less than 40 when evaporation rate makes the evaporation rate of butyl acetate 100. The evaporation rate of the solvent (E2) is preferably 25 or more and less than 40, and more preferably 30 or more and less than 40.

Examples of the solvent (E2) include ethylene glycol monoethyl ether (evaporation rate: 32), ethylene glycol monopropyl ether (evaporation rate: 20), ethylene glycol monobutyl ether (evaporation rate: 19), and propylene glycol monopropyl ether (evaporation rate: Ether solvents such as 21);

Ester solvents such as methyl lactate (evaporation rate: 29), ethyl lactate (evaporation rate: 22), ethyl pyruvate (evaporation rate: 31);

3-methoxybutyl acetate (evaporation rate: 14), propylene glycol monomethyl ether acetate (evaporation rate: 33), propylene glycol monoethyl ether acetate (evaporation rate: 19), propylene glycol monomethyl ether propionate (evaporation rate : 19), ether ester solvents such as ethylene glycol monomethyl ether acetate (evaporation rate: 31), ethylene glycol monoethyl ether acetate (evaporation rate: 21), and methyl 3-methoxypropionate (evaporation rate: 32);

Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (evaporation rate: 15), diisobutyl ketone (evaporation rate: 20), and cyclohexanone (evaporation rate: 23);

Amide solvents, such as N, N- dimethylformamide (evaporation rate: 17), are mentioned.

Among them, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether and methyl 3-methoxypropionate are preferable, and propylene glycol monomethyl ether acetate is more preferable.

Content of each solvent in a solvent (E) is each with respect to the total amount of a solvent (E).

Dialkylene glycol dialkyl ethers; 1 to 45 mass%

Solvent (E1); 5 to 80 mass%

Solvent (E2); 5-80 mass% is preferable,

Dialkylene glycol dialkyl ethers; 10-40 mass%

Solvent (E1); 10 to 70 mass%

Solvent (E2); 10-70 mass% is more preferable.

Preferably the evaporation rate of the solvent (E) which is a mixed solvent is 55 or more and 90 or less, More preferably, it is 55 or more and 85 or less, More preferably, it is 55 or more and 80 or less. The evaporation rate of the solvent (E) can be measured by the method mentioned above. When the evaporation rate of a solvent (E) is in the said range, the drying time at the time of drying under reduced pressure is short, and especially the flatness of the film | membrane obtained by apply | coating curable resin composition is high.

Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of 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 obtained by apply | coating curable resin composition to high.

&Lt; Other components >

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

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

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

2,2'- azobis (2-methylvaleronitrile), 2,2'- azobis (2, 4- dimethylvaleronitrile), etc. are mentioned as a thermal radical generating agent.

As a ultraviolet absorber, 2- (3-tert- butyl- 2-hydroxy-5- methylphenyl) -5-chloro benzotriazole, alkoxy benzophenone, etc. are mentioned.

Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 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-aminopropyltrimeth Methoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3- The unexposed propyl triethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane, a N- phenyl-3-aminopropyl, and the like silane.

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 usually 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% or more. More preferably, it is 80% or more.

When the curable resin composition of this invention is used as a cured film, the average transmittance of a cured film becomes like this. Preferably it is 90% or more, More preferably, it is 95% or more. This average transmittance | permeability is an average value when it measures on the cured film whose thickness after heat-hardening (100-250 degreeC, 5 minutes-3 hours) is 2 micrometers on the conditions of the measurement wavelength 400-700 nm using a spectrophotometer. Thereby, the cured film excellent in transparency in visible region can be provided.

<The manufacturing method of a curable resin composition>

Curable resin composition of this invention is a (meth) acryl compound (B), an epoxy resin (C), a polymerization initiator (D), a polymerization start adjuvant (D1) used as needed, and resin (A) and a solvent (E), It can manufacture by mixing antioxidant (F), surfactant (H), polyhydric carboxylic acid (G), imidazole compound (J), and other components by a well-known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 µm.

<Manufacturing Method of Cured Film>

A cured film can be manufactured by apply | coating curable resin composition of this invention on a board | substrate, and hardening by heat.

More specifically, the manufacturing method of the cured film of this invention includes the following process (1)-process (3).

Process (1) Process of apply | coating curable resin composition of this invention to board | substrate

Process (2) The process of forming the composition layer by drying under reduced pressure the applied curable resin composition

Process (3) The process of heating a composition layer

Moreover, when curable resin composition of this invention contains a polymerization initiator (D), the cured film which has a pattern can be manufactured by performing the following process.

Process (1) Process of apply | coating curable resin composition of this invention to board | substrate

Process (2) The process of forming the composition layer by drying under reduced pressure the applied curable resin composition

Process (2a) Process of exposing composition layer through photomask

Process (2b) Process of developing composition layer after exposure

Process of heating the composition layer after process (3a) image development

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

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

Application | coating on a board | substrate is performed using coating apparatuses, such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, and a dip coater.

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

Drying under reduced pressure is preferably performed at a temperature in the range of 20 to 25 ° C. under a pressure of 50 to 150 Pa.

You may perform heat drying (prebaking) before or after drying under reduced pressure. Heat drying is normally performed using heating apparatuses, such as an oven and a hotplate. 30-120 degreeC is preferable and, as for the temperature of heat drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-30 minutes.

Step (3) is a step (post bake) of heating the composition layer. By heating, the composition layer is cured to form a cured film. Heating is usually performed using heating apparatuses, such as an oven and a hotplate. 150-250 degreeC is preferable and 160-235 degreeC of heating temperature is more preferable. 1 to 120 minutes are preferable and, as for a heat time, 10 to 60 minutes are more preferable.

Step (2a) is a step of exposing the composition layer formed by step (2) through a photomask. As the photomask, a light shielding portion is formed corresponding to a portion of the composition layer to be removed. The shape of the light shielding portion is not particularly limited and can be selected according to the intended use.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. You may do it. As a light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since the parallel light beam can be irradiated uniformly to the whole exposure surface or the exact alignment of a photomask and a composition layer can be carried out.

Process (2b) is a process of developing the composition layer after exposure. By developing the composition layer after exposure in contact with the developer, the unexposed portion of the composition layer is dissolved in the developer and removed, thereby forming a composition layer having a pattern on the substrate.

As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method and a spray method. In addition, during development, the substrate may be tilted at an arbitrary angle.

It is preferable to wash with water after image development.

Step (3a) is a step of heating the composition layer after development. By heating similarly to the said process (3), the composition layer which has a pattern is hardened | cured, and the cured film which has a pattern is formed on a board | substrate.

The cured film thus obtained has a short time and particularly excellent flatness in the drying step, and thus, for example, as a protective film or overcoat of a color filter substrate, a touch panel used for a liquid crystal display device, an organic EL display device or an electronic paper. useful. Thereby, it becomes possible to manufacture the display apparatus provided with a high quality cured film with high productivity.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example are mass% and a mass part, unless there is particular notice.

Synthesis Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring. Then 40 parts methacrylic acid; And a mixture of monomer (I-1) and monomer (II-1) (molar ratio of monomer (I-1) to monomer (II-1) in the mixture = 50:50} 360 parts of diethylene glycol ethylmethyl ether in 190 parts The solution which melt | dissolved 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 ether was dripped in the flask over 5 hours using the other dropping pump. . After dripping of the polymerization initiator solution was complete | finished, it hold | maintained at 70 degreeC for 4 hours, and it cooled to room temperature after that, and obtained the copolymer (resin Aa) solution of 42.3% of solid content. As for the weight average molecular weight (Mw) of obtained resin Aa, the acid value of 1.91 and solid content conversion of 8000 and molecular weight distribution (Mw / Mn) was 60 mg-KOH / g. Resin Aa has the following structural units.

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.

Device: K2479 (manufactured by Shimadzu Seisakusho Co., Ltd.)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector: RI

Calibration standard: 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.

Examples 1-5 and Comparative Example 1

<Preparation of curable resin composition>

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

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

Resin (A); Aa; Resin Aa

(Meth) acrylic compound (B); Dipentaerythritol hexaacrylate (KAYARAD® DPHA; manufactured by Nihon Kayaku Co., Ltd.)

Epoxy resin (C); Bisphenol A type epoxy resin (JER157S70; Mitsubishi Chemical Co., Ltd. make)

Polymerization initiator (D); Da; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IRGACURE® OXE01; manufactured by BASF; O-acyl oxime compound)

Polymerization initiator (D); Db; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; manufactured by Hodogaya Chemical Co., Ltd .; Dazole compounds)

Polymerization initiation aid (D1); 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline (compound represented by the following formula)

Thiol compound (T); Pentaerythritol tetrakis propionate (PEMP; manufactured by SC Yuki Chemical Co., Ltd.)

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

Polyhydric carboxylic acid (G); Butanetetracarboxylic acid (Rikacid BT-W; manufactured by Shin-Nihon Rica Co., Ltd.)

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

Surfactant (H); Polyether modified silicone oil (Toray Silicone SH8400; Toray Dow Corning Co., Ltd. product)

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

Solvent (E); Eb; Propylene Glycol Monomethyl Ether (Evaporation Rate: 62)

Solvent (E); Ec; Propylene Glycol Monomethyl Ether Acetate (Evaporation Rate: 33)

Solvent (E); Ed; 3-methoxy-1-butanol (evaporation rate: 12)

The solvent (E) is mixed so that the solid content of the curable resin composition becomes the "solid content (%)" in Table 1, and the values of the solvent components (Ea) to (Ed) in the solvent (E) are the mass ratios ( %).

<Measurement of solvent evaporation rate>

In the hood which made it possible to supply nitrogen gas, chemical balance and filter paper No. Two 70 mm diameter chalets containing 2 (70 mm diameter) were provided, and n.butyl acetate was added to one side, and 1.0.g each was put into the other side. In the hood, nitrogen gas was supplied at a flow rate of 30 NL / ml, and the weight of n-butyl acetate and the sample was measured at the same time every 60 seconds, and the evaporation rate was determined from the weight at 60, 120, and 180 seconds. Were respectively calculated. These average values were made into the evaporation rate of a sample.

Table 2 shows the evaporation rate when the evaporation rate of butyl acetate which measured the solvent (E) contained in the curable resin composition of an Example and a comparative example as 100 is 100.

<Viscosity measurement>

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

<Measurement of transmittance of the composition>

Average transmittance (%) in 400-700 nm using the ultraviolet-visible near-infrared spectrophotometer (V-650; Nihon Bunco Co., Ltd. product) (quartz cell, optical path length; 1 cm) about the obtained curable resin composition, respectively. Was measured. The results are shown in Table 4.

<Production of Curing Film>

A square glass substrate (Eagle XG; manufactured by Corning) having one side of 2 inches was washed sequentially with a neutral detergent, water, and isopropanol, and dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after postbaking might be set to 2.0 micrometers, and then prebaked for 10 minutes at 90 degreeC in the clean oven. Then, it post-baked for 40 minutes at 230 degreeC, and obtained the cured film.

&Lt; Measurement of film thickness &

The film thickness of the cured film was measured at a measuring width of 500 µm and a measuring speed of 10 seconds using a contact type film thickness measuring apparatus (DEKTAK6M; manufactured by ULVAC Co., Ltd.).

<Measurement of transmittance of the cured film>

The obtained cured film measured the transmittance | permeability (%) in 400 nm, and the average transmittance | permeability (%) in 400-700 nm using the microscopic spectrophotometer (OSP-SP200; OLYMPUS Corporation). The results are shown in Table 4.

<Evaluation of reduced pressure drying time>

The curable resin composition was apply | coated on the conditions which the film thickness after post-baking will be 15 micrometers using the slit die coater (made by Takudai-100 Itutochuki Co., Ltd.) on the square ITO film-forming glass substrate whose one side is 15 cm. Thereafter, the rotary pump rotation speed was measured using a decompression dryer (manufactured by VCD Microtech Co., Ltd.) at 1000 rpm, booster pump rotation speed 700 rpm, and normal pressure of 25 ° C until the decompression degree reached 66 Pa. . If the reduced pressure drying time is short, the productivity of the cured film is increased, which is advantageous. The results are shown in Table 4.

<Slit nozzle dryness evaluation>

The curable resin composition was subjected to post-baking film thickness of 1.5 µm using a slit die coater (Takudai-100; manufactured by Itochusanki Co., Ltd.) on a glass substrate on which a square ITO was formed on one side of 15 cm. Applied.

Thereafter, the nozzle of the slit die coater is left as it is for 1 minute, and then, without washing the tip of the nozzle, the curable resin composition is formed on a glass substrate having a square ITO film of 15 cm on one side as described above. Applied.

The substrate to which the curable resin composition was applied without washing the tip of the nozzle was dried under reduced pressure until the reduced pressure reached 0.5 torr with a reduced pressure drier (manufactured by VCD Microtech Co., Ltd.), and then free at 90 ° C. for 2 minutes on a hot plate. It baked and the composition layer was formed.

After cooling, the composition layer surface was observed by visually confirming the surface of the composition layer with a Na lamp.

When the vertical stripe unevenness could be confirmed clearly, (triangle | delta) and the case where it was not able to confirm slightly were made into (circle). The results are shown in Table 4.

Flatness evaluation; Fabrication of Evaluation Boards>

Each component shown in Table 3 was mixed in the ratio shown in Table 3, and the coloring photosensitive resin composition was obtained.

C.I. Pigment Blue 15: 6 Part 5.48 C.I. Pigment Violet 23 0.35part Pigment dispersant 2.04 part Benzyl methacrylate / methacrylic acid copolymer (mass composition ratio: 65/35, polystyrene conversion weight average molecular weight: 25000) Part 7.38 Dipentaerythritol hexaacrylate (Nihon Kayaku Co., Ltd. KAYARAD DPHA) Part 7.38 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (IRGACURE 369 made by BASF) Part 1.77 4,4'- diethylamino benzophenone (Hodogaya Chemical Co., Ltd. make EAB-F) 0.59part Polyether modified silicone oil (Toray Silicone SH8400 manufactured by Toray Dow Corning) 0.01 part Ethyl 3-ethoxypropionate Part 15 Propylene glycol monomethyl ether acetate 60 copies

A glass substrate on which a square of ITO having a thickness of 15 cm on one side was formed was washed sequentially with a neutral detergent, water, and isopropanol, and dried. On this board | substrate, the coloring photosensitive resin composition was spin-coated so that the film thickness after postbaking might be set to 1.6 micrometers. Subsequently, it prebaked for 3 minutes at 90 degreeC in the clean oven, and formed the coloring composition layer. After cooling, 1000 mJ was used under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) at an interval of 100 μm between the colored composition layer on the substrate and the quartz glass photomask. The light was irradiated at an exposure amount (365 nm standard) of / cm 2. On the other hand, this light irradiation was performed by passing the light emitted from an ultrahigh pressure mercury lamp through an optical filter (UV-35; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a line & space pattern having a line width of 30 µm was used. The colored composition layer after light irradiation was developed by immersing for 80 seconds at 23 ° C. for 80 seconds with an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide. After washing with water, post-baking was performed at 220 ° C. for 20 minutes. , The evaluation board | substrate with which the coloring pattern of the line & space of 30 micrometers of line widths was formed was created.

When the film thickness of the formed coloring pattern was measured, it confirmed that it was 1.6 micrometers.

<Evaluation of Flatness 1>

The curable resin composition was apply | coated to the said board | substrate for evaluation using the slit die coater (made by Takudai-100 Itutochuki Co., Ltd.) on condition that the film thickness after postbaking might be 1.5 micrometers. Then, it dried under reduced pressure until the pressure reduction degree became 0.5 torr by the pressure reduction dryer (made by VCD Microtech Co., Ltd.), and prebaked at 90 degreeC for 2 minutes on the hotplate. After cooling, the cured film was formed by post-baking at 230 degreeC for 40 minutes.

The film thickness was measured in the part in which the coloring pattern is not formed under a cured film among the cured films on the evaluation board | substrate, and confirmed that it was 1.5 micrometers.

The height difference of the relief of the surface of the cured film formed on the coloring pattern was measured. If this height difference is 0.5 micrometer or less, the flatness of a cured film is favorable and it can be said that it is especially useful as a protective film for color filters. The results are shown in Table 4.

<Evaluation of Flatness 2>

The curable resin composition was apply | coated to the said board | substrate for evaluation using the slit die coater (made by Takudai-100 Itutochuki Co., Ltd.) on condition that the film thickness after postbaking might be 1.5 micrometers. Then, it dried under reduced pressure until the pressure reduction degree became 0.5 torr by the pressure reduction dryer (made by VCD Microtech Co., Ltd.), and prebaked at 90 degreeC for 2 minutes on the hotplate. After cooling, light was irradiated at an exposure amount of 250 mJ / cm 2 (365 nm standard) under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., a light source; ultra-high pressure mercury lamp). On the other hand, this light irradiation was performed by passing the light emitted from an ultrahigh pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). The composition layer after light irradiation was immersed and developed at 25 degreeC for 60 second with the aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, and after washing with water, it post-baked at 230 degreeC for 20 minutes, and the cured film was formed.

The film thickness was measured in the part in which the coloring pattern is not formed under a cured film among the cured films on the evaluation board | substrate, and confirmed that it was 1.5 micrometers.

The height difference of the relief of the surface of the cured film formed on the coloring pattern was measured. If this height difference is 0.5 micrometer or less, the flatness of a cured film is favorable and it can be said that it is especially useful as a protective film for color filters. The results are shown in Table 4.

<Resolution evaluation>

As a substrate, using a square glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) having one side of 2 inches, and exposing light at a light exposure amount (365 nm standard) of 100 mJ / cm 2 through a photomask, the flatness evaluation 2 and In the same manner, a cured film having a pattern was produced. In addition, as a photomask, the mask in which the 20 micrometer line & space pattern was formed was used.

The said pattern was observed using the obtained cured film scanning electron microscope (S-4000; the product made by Hitachi High-Technologies Co., Ltd.), and it was set as (circle) when 20 micrometer line & space was resolving, and it was not resolving. The results are shown in Table 4.

 From the result of Table 4, it was confirmed that the curable resin composition of this invention is short in a reduced pressure drying time, and the cured film was excellent also in flatness. Therefore, according to curable resin composition of this invention, productivity is good and a high performance cured film can be manufactured.

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

Claims (6)

Including resin and solvent which have curability,
The solvent contains a dialkylene glycol dialkyl ether, the following solvent (E1), and the following solvent (E2),
Curable resin composition whose content of dialkylene glycol dialkyl ether is 1 mass% or more and 45 mass% or less with respect to the total amount of a solvent.
Solvent (E1): The solvent which is different from dialkylene glycol dialkyl ether and is 40 or more and 100 or less when evaporation rate makes evaporation rate of butyl acetate 100.
Solvent (E2): A solvent which is different from dialkylene glycol dialkyl ether and whose evaporation rate is equal to or greater than 13 and less than 40 when the evaporation rate of butyl acetate is 100. The structural unit according to claim 1, wherein the resin having curability is a structural unit derived from one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and ethylenic unsaturated. Curable resin composition which is a copolymer containing the structural unit derived from the monomer which has a bond. The curable resin composition according to claim 1 or 2, further comprising an antioxidant. The cured film formed from the curable resin composition in any one of Claims 1-3. The display apparatus containing the cured film of Claim 4. (1) Process of apply | coating curable resin composition of any one of Claims 1-3 to a board | substrate,
(2) drying the applied curable resin composition under reduced pressure to form a composition layer, and
(3) step of heating the composition layer
Method for producing a cured film comprising a.