KR20100054727A - Hardening resin composition - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to apply the composition to a display device for forming a coating layer or a pattern, and to improve the transmissivity of the coating layer and the pattern using a printing method. CONSTITUTION: A curable resin composition(2) contains a binder resin, a polymerizable compound, and a solvent. The content rate of the solvent is 20~60mass% for the total amount of the composition. The binder resin is a copolymer formed by polymerizing a compound selected from the group consisting of carboxylic acid and unsaturated carboxylic anhydride, and a monomer with a cyclic ether structure and the carbon number of 2~4. The boiling point of the solvent is over 200 deg C.

Description

Curable Resin Composition {HARDENING RESIN COMPOSITION}

The present invention relates to a curable resin composition, a coating film, a pattern, and a display device.

It is proposed to form a spacer (photo spacer) by photolithography using photosensitive resin between a color filter constituting a display device such as a liquid crystal display device or a touch panel and an array substrate. According to this method, a spacer can be formed in arbitrary places. As a composition used for photolithography, the photosensitive resin composition containing binder resin, a photopolymerizable compound, a photoinitiator, and a solvent is known (patent document 1).

However, in such photolithography, since the pattern of the spacer is formed through a process such as film production, exposure, development, etc., the process is long, complicated, and a large-scale manufacturing facility is required.

As a method other than photolithography, a method of forming a pattern by applying a liquid ink containing a curable resin composition to a specific position on a printed substrate by a printing method such as an inkjet printing method or a flexographic printing method is known (patent) Document 2).

Patent Document 1: Japanese Unexamined Patent Publication No. 2006-171160

Patent Document 2: Japanese Unexamined Patent Publication No. 2008-158284

However, the amount of the solvent contained in the photosensitive resin composition of patent document 1 is 60 mass% or more with respect to the whole composition, and the amount of the solvent contained in the curable resin composition described in patent document 2 is 80 mass% or more with respect to the whole composition. It is not always easy to use it for the printing method, because a long time is required for drying to remove the solvent after printing, or the shape may change after printing or during drying.

An object of the present invention is to provide a curable resin composition capable of forming a coating film or a pattern having a high transmittance by a printing method.

MEANS TO SOLVE THE PROBLEM As a result of examining in order to find out the curable resin composition which can solve the said subject, the coating film of the high transmittance | permeability by printing method is made by making the quantity of the solvent contained 20 mass% or more and less than 60 mass% with respect to the whole composition. Or it discovered that the curable resin composition which can form a pattern was obtained, and reached this invention.

That is, this invention provides the following [1]-[16].

[1] containing a binder resin (A), a polymerizable compound (B) and a solvent (D),

Curable resin composition whose amount of solvent (D) with respect to the total amount of binder resin (A), a polymeric compound (B), and a solvent (D) is 20 mass% or more and less than 60 mass%.

[2] The curable resin composition according to the above [1], wherein the amount of the solvent (D) to the total amount of the binder resin (A), the polymerizable compound (B), and the solvent (D) is 25% by mass to 50% by mass.

[3] a monomer (Ac) having at least one compound selected from the group consisting of at least an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa) and a cyclic ether having 2 to 4 carbon atoms Curable resin composition as described in said [1] or [2] which is a copolymer formed by superposing | polymerizing.

[4] The curable resin composition according to the above [3], wherein the monomer (A-c) having a cyclic ether having 2 to 4 carbon atoms is a monomer having an epoxy group.

[5] The curable resin composition according to the above [4], wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group.

[6] The curable resin composition according to the above [5], wherein the monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II).

[In formula (I) and formula (II), R <_1> and R <_2> represents a hydrogen atom or a C1-C4 alkyl group each independently. The hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ₁ and X ₂ each independently represent a C 1-6 alkylene group which may contain a single bond or a hetero atom;

[7] at least one compound selected from the group consisting of aliphatic unsaturated carboxylic acids and aliphatic unsaturated carboxylic anhydrides, at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Aa) Curable resin composition in any one of said [3]-[6] which is a compound.

[8] a group consisting of a compound represented by formula (I ') and at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) Curable resin composition as described in said [6] which is at least 1 sort (s) of compound chosen from.

In formula (I ') and formula (II'), R <_1>'and R <_2>' respectively independently represent a hydrogen atom or a C1-C4 alkyl group. The hydrogen atom contained in this alkyl group may be substituted by the hydroxy group]

[9] The solvent [D], wherein the solvent (D) is a solvent having a boiling point of 200 ° C. or more and containing at least one solvent selected from the group consisting of ester solvents, ether solvents, and alcohol solvents. Curable resin composition in any one of.

[10] The curable resin composition according to any one of the above [1] to [9], further containing a polymerization initiator (C).

[11] a polymerization initiator wherein the polymerization initiator (C) contains at least one compound selected from the group consisting of a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound and an oxime compound Curable resin composition as described in said [10].

[12] Use of the curable resin composition according to any one of the above [1] to [11] for forming a coating film or a pattern.

[13] A coating film or pattern formed by using the curable resin composition according to any one of the above [1] to [11].

[14] A display device containing the coating film or pattern according to the above [13].

[15] A method for producing a coating film or pattern, which has a step of applying the curable resin composition according to any one of the above [1] to [11] onto a substrate using a printing method, drying and heating to obtain a coating film or pattern. .

[16] The curable resin composition according to any one of the above [1] to [11] is coated on a substrate using a printing method, dried, and subjected to exposure treatment, and further heated as necessary to obtain a coating film or a pattern. The manufacturing method of the coating film or pattern which has a process.

Curable resin composition of this invention can form the coating film or pattern of high transmittance | permeability by the printing method.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Curable resin composition of this invention contains binder resin (A), a polymeric compound (B), and a solvent (D), and is a solvent with respect to the total amount of binder resin (A), a polymeric compound (B), and a solvent (D). The amount of (D) is 20 mass% or more and less than 60 mass%.

As binder resin (A) used for curable resin composition of this invention, binder resin (A1) and binder resin (A2) are illustrated. Binder resin (A1) has an acidic group, binder resin (A2) has an acidic group, and shows the reactivity by the action of at least one of light and heat.

If the binder resin has an acidic group, the Tg and the mechanical properties of the binder resin tend to be high, which is preferable. Moreover, when it contains as a copolymer component the monomer (A-c) which has a C2-C4 cyclic ether structural group, it is preferable because it has a tendency for hardenability to become high and chemical resistance and heat resistance become high.

As binder resin (A1), it is copolymerizable with at least 1 sort (Aa) (Hereinafter, it may be called "(Aa)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (Aa). The copolymer etc. of a monomer (Ab) (except (Aa)) (hereinafter may be called "(Ab)") are illustrated.

As (A-a), an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic anhydride etc. are mentioned, for example, Specifically,

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

And anhydrides of the above unsaturated dicarboxylic acids;

Unsaturated mono [(meth) acryloyloxyalkyl of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

-(히드록시메틸)아크릴산 등의, 동일 분자 중에 히드록시기 및 카르복시 기를 함유하는 불포화 아크릴레이트류 등을 들 수 있다.

Unsaturated acrylate containing a hydroxyl group and a carboxy group in the same molecule, such as-(hydroxymethyl) acrylic acid, etc. are mentioned.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used in terms of good copolymerization reactivity, high Tg and mechanical properties of the copolymer, and no tackiness. These are used alone or in combination.

As (A-b),

(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, dicyclopentanyl as conventional name) (Meth) acrylic-acid cyclic alkyl esters, such as (meth) acrylate), dicyclopentanyloxyethyl (meth) acrylate, and isoboroyl (meth) acrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (also known in the art as dicyclopentanyl acrylate), dicyclopentaoxy Acrylic acid cyclic alkyl esters such as ethyl acrylate and isoboroyl acrylate;

(Meth) acrylic acid aryl esters, such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2 '-Hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene , 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) Bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2 2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydrate Hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene , 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclo Hexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo Bicyclo unsaturated compounds, such as [2.2.1] hepto-2-ene and 5, 6- di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

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

-메틸스티렌, m-메틸스티렌, p-메틸스티렌, 비닐톨루엔, p-메톡시스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화비닐, 염화비닐리덴, 아크릴아미드, 메타크릴아미드, 아세트산비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔 등을 들 수 있다. Styrene,

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

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferable in terms of copolymerization reactivity and alkali solubility.

(A-a) and (A-b) are used alone or in combination.

In addition, in this specification, (meth) acrylate means an acrylate and / or a methacrylate.

In the copolymer obtained by copolymerizing (Aa) and (Ab), when the ratio of the constituent component derived from each makes the total mole number of the constituent component which comprises the said copolymer into 100 mol%, it is a mole fraction below. It is preferable to be in a range.

Structural units derived from (A-a); 2-40 mol%

Structural units derived from (A-b); 60 to 98 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

Structural units derived from (A-a); 5 to 35 mol%

Structural units derived from (A-b); 65 to 95 mol%

When the said composition ratio exists in the said range, there exists a tendency for storage stability and solvent resistance to become favorable.

The binder resin (A1) is described in, for example, the method described in the document "Experimental Method of Polymer Synthesis" (first edition, March 1, 1972, first edition of Otsu Takayuki Kogyo Co., Ltd.). It can manufacture with reference to the cited document.

Specifically, a predetermined amount of the units (Aa) and (Ab) constituting the copolymer, a polymerization initiator, and a solvent are injected into the reaction vessel, and oxygen is substituted with nitrogen to stir, heat, and keep warm in the absence of oxygen. A polymer is obtained. In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

The weight average molecular weight of polystyrene conversion of binder resin (A1) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin (A1) which has an acidic group exists in the said range, applicability | paintability tends to become favorable, Tg and mechanical property of binder resin tend to become high, and it is preferable in the tendency for tackiness to disappear.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of binder resin (A1) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. If molecular weight distribution exists in the said range, since it exists in the tendency for applicability | paintability excellent, it is preferable.

Content of binder resin (A1) which can be used for curable resin composition of this invention is a mass fraction with respect to solid content in curable resin composition, Preferably it is 5-90 mass%, More preferably, it is 10-70 mass%. When content of binder resin (A1) exists in the said range, there exists a tendency for favorable printability and it is preferable.

As binder resin (A2) which has an acidic group and shows reactivity by the action of at least one of light and heat, (A2-1)-(A2-3) is illustrated.

Binder resin (A2-1) is a copolymer of (A-a), (A-b), and the monomer (A-c) (Hereinafter, it may be called "(A-c)") which has a C2-C4 cyclic ether structure.

In the copolymer of (Aa) and (Ab), the binder resin (A2-2) is made by reacting a part of the carboxyl group derived from (Aa) with a cyclic ether structure having 2 to 4 carbon atoms derived from (Ac). It is a copolymer obtained.

Binder resin (A2-3) is a copolymer of (A-a) and (A-c).

(Ac) is a polymerizable compound having at least one structure selected from the group consisting of, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxirane structure, an oxetane structure, and a tetrahydrofuran structure). The monomer (Ac) having a cyclic ether structure having 2 to 4 carbon atoms has at least one structure selected from the group consisting of cyclic ether structures having 2 to 4 carbon atoms, and also has a carbon-carbon unsaturated bond. It is preferable that it is a compound, it is a compound which has at least 1 sort (s) of structure chosen from the group which consists of a C2-C4 cyclic ether structure, and has acryloyl group or a methacryloyl group.

As (A-c), the monomer which has an epoxy group, the monomer which has an oxetanyl group, the monomer which has tetrahydrofuryl group, etc. are mentioned, for example.

The monomer which has the said epoxy group means the polymeric compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic epoxy group and an alicyclic epoxy group, for example. The monomer having the epoxy group is a compound having at least one group selected from the group consisting of aliphatic epoxy groups and alicyclic epoxy groups, and also having a carbon-carbon unsaturated bond, and selected from the group consisting of aliphatic epoxy groups and alicyclic epoxy groups. It is more preferable that it is a compound which has at least 1 type of structure, and has acryloyl group or a methacryloyl group.

Herein, the aliphatic epoxy group refers to a monocyclic oxylanyl group, and the alicyclic epoxy group refers to a group having a structure in which an alicyclic hydrocarbon ring and an oxirane ring are condensed.

As a compound which has an aliphatic epoxy group among the monomer which has the said epoxy group, specifically, glycidyl (meth) acrylate, (beta) -methyl glycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate , Glycidyl vinyl ether, and the compound represented by the following formula described in JP-A-7-248625.

(In formula, R <^11> -R <^13> is a hydrogen atom or a C1-C10 alkyl group each independently, and m is an integer of 1-5.)

-메틸-o-비닐벤질글리시딜에테르,

-메틸-m-비닐벤질글리시딜에테르,

-메틸-p-비닐벤질글리시딜에테르, 2,3-디글리시딜옥시메틸스티렌, 2,4-디글리시딜옥시메틸스티렌, 2,5-디글리시딜옥시메틸스티렌, 2,6-디글리시딜옥시메틸스티렌, 2,3,4-트리글리시딜옥시메틸스티렌, 2,3,5-트리글리시딜옥시메틸스티렌, 2,3,6-트리글리시딜옥시메틸스티렌, 3,4,5-트리글리시딜옥시메틸스티렌, 2,4,6-트리글리시딜옥시메틸스티렌 등을 들 수 있다.As a compound represented by the said formula, For example, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,

-Methyl-o-vinylbenzylglycidyl ether,

Methyl-m-vinylbenzylglycidyl ether,

-Methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2, 6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3 , 4,5-triglycidyloxymethyl styrene, 2,4,6-triglycidyloxymethyl styrene, and the like.

As a monomer which has an alicyclic epoxy group, the monomer which has an aliphatic monocyclic epoxy group, the monomer which has an aliphatic polycyclic epoxy group, etc. are mentioned among the monomer which has the said epoxy group.

The monomer which has the said aliphatic monocyclic epoxy group means the polymeric compound which has a structure which the ring and the oxirane ring of the monocyclic alicyclic hydrocarbon condensed. It is preferable that the monomer which has the said aliphatic monocyclic epoxy group is a compound which the ring and oxirane ring of the monocyclic alicyclic hydrocarbon condensed, and also has a carbon-carbon unsaturated bond, and the ring and oxy of the monocyclic alicyclic hydrocarbon It is more preferable that it is a compound which has a structure which a column ring condensed, and has acryloyl group or a methacryloyl group.

As a ring of the alicyclic hydrocarbon of the said monocyclic ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring etc. are mentioned, for example, A C4-C6 ring is especially preferable.

Specific examples of the monomer having an aliphatic monocyclic epoxy group include vinylcyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (eg, serotoside 2000;

Daicel Chemical Industry Co., Ltd.), 3, 4- epoxycyclohexyl methyl acrylate (for example, cycloma A400; Daicel Chemical Industry Co., Ltd. product), 3, 4- epoxycyclohexyl methyl methacrylate (For example, cyclochrom M100; Daicel Chemical Industry Co., Ltd. product) etc. are mentioned.

The monomer which has the said aliphatic polycyclic epoxy group means the polymeric compound which has a structure which the ring and the oxirane ring of the polycyclic alicyclic hydrocarbon condensed. The monomer having a structure in which the ring and the oxirane ring of the polycyclic alicyclic hydrocarbon are condensed has a structure in which the ring and the oxirane ring of the polycyclic alicyclic hydrocarbon are condensed, and is a compound having a carbon-carbon unsaturated bond. It is preferable that it is a compound which has a structure which the ring of the polycyclic alicyclic hydrocarbon and the oxirane ring condensed, and has acryloyl group or methacryloyl group.

As a ring of the alicyclic hydrocarbon of the said polycyclic ring, a dicyclopentane ring, a tricyclodecane ring, a norbornane ring, an isononorbornane ring, a bicyclooctane ring, a bicyclononane ring, a bicycloound And a cyclo ring, a tricyclo undecane ring, a bicyclo dodecane ring, a tricyclo dodecane ring, etc. are mentioned, Especially, a C8-C12 compound is preferable.

As a monomer which has the said aliphatic polycyclic epoxy group, at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II), etc. are mentioned, for example.

In Formula (I) and Formula (II), R <_1> and R <_2> respectively independently represents the C1-C4 alkyl group which may be substituted by the hydrogen atom or hydroxy.

X ₁ and X ₂ each independently represent a C 1-6 alkylene group which may contain a single bond or a hetero atom.

As R ₁ and R ₂ , specifically, a hydrogen atom; Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy -Isopropyl group, 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n And hydroxyl group-containing alkyl groups such as -butyl group. Especially, Preferably a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

As X ₁ and X ₂ , specifically, a single bond; Alkylene groups such as methylene group, ethylene group and propylene group;

Hetero atom containing alkylene groups, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group, an aminopropylene group, etc. are mentioned. Especially, Preferably, a single bond, a methylene group, ethylene group, an oxymethylene group, and an oxyethylene group are mentioned, More preferably, a single bond and an oxyethylene group are mentioned.

As at least 1 type of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II), it consists of a compound represented by following formula (I ') and a compound represented by Formula (II'). It is preferable that it is at least 1 type of compound chosen from the group.

In formula (I ') and formula (II'), R <_1>'and R <_2>' are synonymous with said R <_1> and R <_2> , respectively.

Specifically as a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned, Preferably, it is Formula (I-1), a formula (I-3), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), and more preferably a formula (I-1), formula (I-7), formula (I-9), and formula (I-15) are mentioned.

As a compound represented by Formula (II), specifically, the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned, Preferably, it is Formula (II-1), a formula (II-3), formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), and more preferably a formula (II-1), formula (II-7), formula (II-9), and formula (II-15).

At least 1 type of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II) can be used independently, respectively, and can be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in a molar ratio, preferably from 5:95 to 95: 5 in the formula (I): formula (II), more preferably from 10:90 to 90:10, still more preferably from 20: It is 80-80: 20.

The monomer which has the said oxetanyl group means the polymeric compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic oxetanyl group and an alicyclic oxetanyl group, for example. It is preferable that the monomer which has the said oxetanyl group is a compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic oxetanyl group and an alicyclic oxetanyl group, and has an unsaturated bond.

Specifically as a monomer which has the said oxetanyl group, 3-methyl-3- methacryloxy methyl oxetane, 3-methyl-3- acryloxy methyl oxetane, 3-ethyl-3- methacryloxy methyl oxetane , 3-ethyl-3-acryloxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane Or 3-ethyl-3-acryloxyethyl oxetane.

These are used alone or in combination.

The monomer which has the said tetrahydrofuryl group means the polymeric compound which has at least 1 sort (s) of group chosen from the group which consists of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group, for example. It is preferable that the monomer which has the said tetrahydrofuryl group is a compound which has at least 1 sort (s) of group chosen from the group which consists of aliphatic tetrahydrofuryl group and alicyclic tetrahydrofuryl group, and has an unsaturated bond.

As a monomer which has the said tetrahydrofuryl group, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, etc. are mentioned specifically ,.

These are used alone or in combination.

In binder resin (A2-1), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises binder resin (A2-1).

Structural units derived from (A-a); 2-40 mol%

Structural units derived from (A-b); 1 to 65 mol%

Structural units derived from (A-c); 2 to 95 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

Derived from (A-a); 5 to 35 mol%

Structural units derived from (A-b); 1 to 60 mol%

Structural units derived from (A-c); 5 to 80 mol%

When the said composition ratio exists in the said range, storage stability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

The binder resin (A2-1) is described in, for example, the method described in the document "Experimental method of polymer synthesis" (first edition March 1, 1972, first edition of Oka Takayuki Kogyo Co., Ltd.) It may be prepared with reference to the cited documents described.

Specifically, a predetermined amount of a compound, a polymerization initiator, and a solvent, which induce units (Aa), (Ab) and (Ac) constituting the copolymer, are injected into the reaction vessel, and oxygen is replaced by nitrogen to reduce the oxygen ratio. The polymer is obtained by stirring, heating, and keeping warm in presence. In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

In manufacturing binder resin (A2-2), a copolymer is manufactured by copolymerizing (A-a) and (A-b) first. It is preferable that the ratio of the component derived from each is in the following ranges in mole fraction with respect to the total mole number of the component which comprises the said copolymer.

Structural units derived from (A-a); 5-50 mol%

Structural units derived from (A-b); 50 to 95 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

Structural units derived from (A-a); 10 to 45 mol%

Structural units derived from (A-b); 55 to 90 mol%

Next, in order to give reactivity by the action of light or heat, a part of the carboxylic acid and carboxylic anhydride of (Aa) derived from the copolymer obtained by copolymerizing (Aa) and (Ab) is (Ac) It reacts with the epoxy group or oxetanyl group derived from

The molar number of (A-c) is 5-80 mol% with respect to the mole number of (A-a), Preferably it is 10-75 mol%, More preferably, it is 15-70 mol%.

When the composition ratio is in the above range, the balance of storage stability, solvent resistance, heat resistance, mechanical strength, and sensitivity (so-called photocurability) tends to be good.

Binder resin (A2-2) can be manufactured through a two-step process. For example, the method described in the document "Experimental method of polymer synthesis" (Otsu Takayuki Kogyo Co., Ltd. first edition first edition March 1, 1972) and Japanese Unexamined Patent Publication No. 2001-89533 It may be prepared by reference to the method.

Specifically, first, the process of the first step will be described. A predetermined amount, a polymerization initiator and a solvent of a compound inducing units (Aa) and (Ab) constituting a copolymer (i.e., binder resin) obtained by copolymerizing (Aa) and (Ab) are injected into a reaction vessel, and nitrogen By substituting oxygen by the above, binder resin is obtained by stirring, heating, and keeping warm in the absence of oxygen. In addition, the obtained resin may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. The weight average molecular weight of polystyrene conversion of the said resin becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin exists in the said range, applicability | paintability tends to become favorable and it is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the said resin becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. If molecular weight distribution exists in the said range, since it exists in the tendency for applicability | paintability excellent, it is preferable.

Next, the process of a 2nd step is described. Subsequently, the atmosphere in the flask was replaced with nitrogen from air, and as a reaction catalyst of 5 to 80 mol% of the component (Ac), carboxyl group, epoxy group or oxetanyl group with respect to the mole number of the component (Aa), For example, trisdimethylaminomethylphenol is 0.001-5% by mass with respect to the total amount of monomers (Aa)-(Ac), and hydroquinone is used as a polymerization inhibitor, for example with respect to the total amount of monomers (Aa)-(Ac). The said resin and a structural component (Ac) can be made to react by putting 0.001 to 5% by mass in a flask and continuing reaction for 1 to 10 hours at 60-130 degreeC. In addition, in the same manner as the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility, polymerization, and the like.

In binder resin (A2-3), it is preferable that the ratio of the structural component guide | induced from each exists in the following ranges with a mole fraction with respect to the total mole number of the structural component which comprises binder resin (A2-3).

Structural units derived from (A-a); 5 to 95 mol%

Structural units derived from (A-c); 5 to 95 mol%

Moreover, it is more preferable if the ratio of the said structural component is the following ranges.

Structural units derived from (A-a); 10 to 90 mol%

Structural units derived from (A-c); 10 to 90 mol%

When the said composition ratio exists in the said range, storage stability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

The binder resin (A2-3) is described in, for example, the method described in the document "Experimental Method for Polymer Synthesis" (first edition, March 1, 1972, first edition of Oka Takayuki Kogyo Co., Ltd.) It may be prepared with reference to the cited documents described.

Specifically, a predetermined amount, a polymerization initiator, and a solvent of a compound for inducing units (Aa) and (Ac) constituting the copolymer are injected into the reaction vessel, and the oxygen is replaced with nitrogen, thereby stirring in the absence of oxygen, A polymer is obtained by heating and keeping warm. In addition, the obtained copolymer may use the solution after reaction as it is, the solution which concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used.

As a polymeric compound (B) contained in curable resin composition of this invention, a monofunctional monomer bifunctional monomer or the other trifunctional or more than trifunctional polyfunctional monomer etc. are mentioned.

As a specific example of a monofunctional monomer, nonyl phenylcarbitol (meth) acrylate, 2-hydroxy-3- phenoxypropyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxy Oxyethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate , Caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate, N-vinylpyrrolidone, and the like.

Moreover, as a specific example of a bifunctional monomer, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, and ethylene glycol di ( Meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate Bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, ethoxylated neopentylglycol di (meth) acrylate or 3-methylpentanediol di (meth) acrylate etc. are mentioned.

Specific examples of other trifunctional or higher polyfunctional monomers 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, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritolpenta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritolhepta ( Meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and reactants of acid anhydride, dipentaery Reactant of rititol penta (meth) acrylate with acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylic Latex, 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 tripentaerythritolhepta (meth) acrylate, Reaction of caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, reactant of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Or caprolactone-modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, and the like.

In addition, in this specification, a caprolactone modification means that the ring-opening body of a caprolactone or a ring-opening polymer is introduce | transduced between the alcohol origin site | part of a (meth) acrylate compound, and a (meth) acryloyloxy group.

In particular, a bifunctional or more than polyfunctional monomer is used preferably. These polymeric compounds (B) can be used individually or in combination of 2 or more types.

The content of the polymerizable compound (B) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, based on the mass fraction with respect to the total amount of the binder resin (A) and the polymerizable compound (B). When content of a polymeric compound (B) exists in the said range, since there exists a tendency for the sensitivity, the smoothness, reliability, and mechanical strength of a sensitivity, a coating film, and a pattern to become favorable, it is preferable.

As a polymerization initiator (C) contained in curable resin composition of this invention, it is a compound which starts superposition | polymerization by action of light or a heat, A biimidazole type compound, an acetophenone type compound, a triazine type compound, an acylphosphine oxide type compound Or an oxime type compound is preferable and a biimidazole type compound is especially preferable because it is excellent in sensitivity.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-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, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), 4,4' And imidazole compounds in which the phenyl group in the 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913, etc.), and the like, and preferably 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'- Traphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2- Methyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) -propan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- ( 3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4- Morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholino phenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4- Bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- ( 4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-meth -4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- ( And oligomers of 4-morpholinophenyl) -butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

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

2,4,6-trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned as said acylphosphine oxide type initiator.

-옥시이미노-1-페닐프로판-1-온, 식 (Ⅳ) 로 나타내는 화합물, 식 (V) 로 나타내는 화합물 등을 들 수 있다.As said oxime compound, O-ethoxycarbonyl-

-Oxyimino-1-phenylpropan-1-one, the compound represented by Formula (IV), the compound represented by Formula (V), etc. are mentioned.

As long as it does not impair the effect of this invention, a photoinitiator etc. can be used together further, and a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, etc. are mentioned as said photoinitiator, for example.

More specifically, the following compounds are mentioned, These can be used individually or in combination of 2 or more types, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, or 1-chloro-, for example 4-propoxy city oxanthone etc. are mentioned.

In addition to this, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like are exemplified as photopolymerization initiators.

Moreover, the photoinitiator described in Unexamined-Japanese-Patent No. 2002-544205 can be used as a photoinitiator which has group which can cause chain transfer.

As a photoinitiator which has the group which can produce the said chain transfer, the photoinitiator of following formula (5)-following formula (10) is mentioned, for example.

Moreover, a light and / or thermal cationic polymerization initiator can be used. An optical and / or thermal cationic polymerization initiator can also use what is comprised from onium cation and an anion derived from Lewis acid.

As a specific example of the said onium cation, diphenyl iodonium, bis (p-tolyl) iodonium, bis (p-tert- butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p- Octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p Isopropylphenyl) iodonium, triphenylsulfonium, tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert Butylphenyl) sulfonium, tris (p-cyanophenyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulphate Phonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyl Oxy) sulfonium, dimethyl (sicle Hexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromopropoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, Dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium, dimethyl (2-hydroxyisopropoxy) sulfonium, or dimethyl (tris (trichloromethyl) methyl) Sulfonium and the like.

Preferred onium cations include bis (p-tolyl) iodium, (p-tolyl) (p-isopropylphenyl) iodium, bis (p-tert-butylphenyl) iodium, triphenylsulfonium or tris ( p-tert-butylphenyl) sulfonium etc. are mentioned.

Specific examples of the anion derived from Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, tetrakis (pentafluorophenyl) borate, and the like. Preferred anions derived from Lewis acids include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

The onium cation and an anion derived from Lewis acid can be arbitrarily combined.

As a specific example of a cationic polymerization initiator, diphenyl iodonium hexafluoro phosphate, bis (p-tolyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) iodonium hexafluoro phosphate, bis ( p-octylphenyl) iodonium hexafluorophosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl Iodide hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluoro Lophosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexaple Orophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, Tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) Sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecaneoxy) sulphate Phosphorous hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclo Pentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexa Fluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, Dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Low phosphate;

Diphenyl iodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl Iodide hexafluoroarsenate, bis (p-octadecylphenyl) iodine hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyl Oxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate , Methylnaphthyl iodonium hexafluoroarsenate, ethylnaphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate Tris (p-isopropylphenyl) sulfonium hexafluoro Recetate, tris (2,6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexa Fluoroarsenate, tris (p-chlorophenyl) sulfoniumhexafluoroarsenate, dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate, dimethyl (methoxy) Sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate , Dimethyl (octyloxy) sulfonium hexafluoroarsenate, dimethyl (octadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-part Methoxy) sulfonium hexafluoro Recetate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarsenate, dimethyl (fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl Iodide hexafluoroantimonate, bis (p-octadecylphenyl) iodine hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyl Oxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate , Methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate Tris (p-isopropylphenyl) sulfonium hexafluoro Antimonate, tris (2,6-dimethylphenyl) sulfoniumhexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium Hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy Sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimo Nate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl (octadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert- Butoxy) sulfonium hexafluoro Timonate, dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-Chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulphate Phonium hexafluoro antimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro antimonate;

Diphenyl iodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluoro Phenyl) borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-octyloxyphenyl Iodide tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluoro Lophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethylnaphthyl iodonium tetra Kiss (pentafluorophenyl) borate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis (pentafluorophenyl) Borate, tris (2,6-dimethylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfoniumtetrakis (pentafluorophenyl) borate, tris (p-cyano Phenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaph Tyl sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (propoxy Sulfonium Tet Lakis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecaneoxy) sulfide Phosphonate tetrakis (pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (Cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluoro Phenyl) borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-sia furnace Methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methyl) sulfonium tetrakis (pentafluorophenyl) Borate, etc., Preferably, bis (p-tolyl) iodonium hexafluoro phosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoro phosphate, bis (p-tert- butylphenyl) is mentioned. Iodinium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p -Tolyl) (p-isopropylphenyl Iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium hexafluoro Loarsenate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) Iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodium tetrakis (pentafluoro Lophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodium, triphenylsulfonium tetrakis (pentafluoro Lophenyl) borate, tris (p-tert-butylphenyl) sulfoniumtetrakis (pentafluor Phenyl) borate etc. are mentioned, More preferably, bis (p-tolyl) iodonium hexafluoro antimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoro antimonate, bis is mentioned. (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p- Tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetra Kiss (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, etc. are mentioned.

Moreover, the polymerization start adjuvant (C-1) can also be used in combination with a polymerization initiator (C), and a polymerization start adjuvant can also be used in multiple combination so that the effect of this invention may not be impaired.

As a polymerization start adjuvant (C-1), an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, the compound represented by Formula (III), the compound represented by Formula (A-1) or Formula (A-2), etc. are mentioned. have.

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanol amine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) or 4,4'-bis (diethylamino Aromatic amine compounds, such as benzophenone, are mentioned.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichlorophenyl And aromatic heteroacetic acids such as thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid.

The polyfunctional thiol compound is a compound having two or more sulfanyl groups in a molecule. Especially, the compound which has two or more sulfanyl groups couple | bonded with the carbon atom of two or more aliphatic hydrocarbon group is more preferable, since the sensitivity of the curable resin composition of this invention becomes high.

Specific examples of the polyfunctional thiol compound include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediolbisthiopropionate, butanediolbisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane Tristhioglycolate, butanediolbisthiopropionate, trimethylolpropanetristiopionopionate, trimethylolpropanetristhioglycolate, pentaerythritol tetrakistiopionopionate, pentaerythritol tetrakisthioglycolate, trishydride Oxyethyltristioff lopionate, pentaerythritol tetrakis (3-mercaptobutylate), 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

Content of a polyfunctional thiol compound is 0.5-20 mass% in mass fraction with respect to a polymerization initiator (C), More preferably, it is 1-15 mass%. When content of a polyfunctional thiol compound exists in the said range, since there exists a tendency for a sensitivity to become high, it is preferable.

As a polymerization start adjuvant (C-1), the compound represented by following formula (III) can also be used.

In Formula (III), the dotted line represented by X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.

Y represents an oxygen atom and a sulfur atom.

R ²¹ represents an alkyl group having 1 to 6 carbon atoms.

R <^22> represents the C1-C12 alkyl group which may be substituted by the halogen atom, or the aryl group which may be substituted by the halogen atom.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

As a C6-C12 aromatic ring which may be substituted by the halogen atom, a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, cyclohexylbenzene Ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring and the like Can be.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n -Propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, etc. are mentioned.

As a C1-C12 alkyl group which may be substituted by the halogen atom, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group , tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1 , 2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3- A chloro-n-butyl group etc. are mentioned.

As an aryl group which may be substituted by the halogen atom, a phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl group, bromophenyl group, dibromo A phenyl group, a naphthyl group, a chloro naphthyl group, a dichloronaphthyl group, a bromonaphthyl group, a dibromonaphthyl group, etc. are mentioned.

Specifically as a compound represented by Formula (III),

2-benzoylmethylene-3-methyl-benzothiazoline,

2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [2,3-d] thiazoline,

2- (2-naphthoylmethylene) -3-methylbenzothiazoline,

2- (1-naphthoylmethylene) -3-methylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,

2- (1-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline,

2- (4-biphenoylmethylene) -3-methylbenzothiazoline,

2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline,

2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline,

2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline,

2-benzoylmethylene-3-methyl-naphtho [2,3-d] oxazoline,

2- (2-naphthoylmethylene) -3-methylbenzooxazoline,

2- (1-naphthoylmethylene) -3-methylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-chlorobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-5-bromobenzooxazoline,

2- (1-naphthoylmethylene) -3-methyl-5-bromobenzooxazoline,

2- (4-biphenoylmethylene) -3-methylbenzooxazoline,

2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzooxazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline,

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, etc. are mentioned.

Among them, 2-benzoylmethylene-3-methyl-naphtho [1,2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by formula (III-1) and formula (III-2) 2-d] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by formula (III-3), 2-benzoylmethylene-3-methyl- Benzothiazoline is preferred.

As a polymerization start adjuvant (C-1), the compound represented by at least 1 sort (s) chosen from the group which consists of a formula (A-1) and a formula (A-2) can also be used.

Of the formula (A-1) and formula (A-2), ring ³¹ and ring X X ³² represents an aromatic ring having 6 to 12 independently of each other. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom. R <^31> and R <^32> represents a C1-C12 alkyl group or a C6-C12 aryl group.

The carbon atom contained in the aromatic ring, the alkyl group or the aryl group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.

Examples of the aromatic ring having 6 to 12 carbon atoms include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, Dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, chrysene ring, Fluoranthene ring, benzo [a] pyrene ring, benzo [e] pyrene ring, perylene ring, derivatives thereof and the like.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl-n-propyl group, 2-methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n -Propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro-n-butyl group, 3-chloro-n-butyl group Etc. can be mentioned.

Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, hydroxyphenyl group, alkoxyphenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl group and bromine A phenyl group, a dibromo phenyl group, a naphthyl group, a chloro naphthyl group, a dichloro naphthyl group, a bromonaphthyl group, a dibromonaphthyl group, a hydroxy naphthyl group, etc. are mentioned.

As a compound represented by a formula (A-1) or a formula (A-2), specifically,

Dialkoxynaphthalenes such as dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene and dibutoxynaphthalene

Dimethoxy anthracene, diethoxy anthracene, dipropoxy canthracene, diisopropoxy canthracene, dibutoxy anthracene, dipentaoxy anthracene, dihexaoxy anthracene, methoxyethoxy anthracene, methoxy propoxy canthracene, methoxy isopropoxy Dialkoxy such as anthracene, methoxybutoxy anthracene, ethoxy propoxycanthracene, ethoxy isopropoxythracene, ethoxy butoxy anthracene, propoxy isopropoxythracene, propoxy butoxy anthracene, isopropoxy butoxy anthracene Anthracene

The dialkoxy naphthacene, such as dimethoxy naphthacene, diethoxy naphthacene, dipropoxy naphthacene, diisopropoxy naphthacene, dibutoxy naphthacene, etc. are mentioned, It is not limited to this.

The content of the polymerization initiator (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the mass fraction with respect to the total amount of the binder resin (A) and the polymerizable compound (B).

Moreover, content of a polymerization start adjuvant (C-1) becomes like this. Preferably it is 0.01-50 mass%, More preferably, it is 0.1-40 mass%.

Content of the compound represented by at least 1 sort (s) chosen from the group which consists of a formula (A-1) and a formula (A-2) becomes like this. Preferably it is 50 to 100% with respect to content of a polymerization start adjuvant (C-1), and Preferably it is 60 to 100%, More preferably, it is 65 to 100%. When content of the compound represented by at least 1 sort (s) chosen from the group which consists of a formula (A-1) and a formula (A-2) exists in the said range, when a coating film is formed using curable resin composition containing this, of a coating film Transparency becomes favorable and is preferable.

When the total amount of the polymerization initiator (C) is in the above range, the curable resin composition becomes highly sensitive, and the strength of the coating film or pattern formed by using the curable resin composition and the smoothness on the surface of the coating film or pattern are It is preferable because it tends to be good. In addition to the above, when the amount of the polymerization initiation assistant (C-1) is in the above range, the sensitivity of the curable resin composition obtained is further increased, and the productivity of the pattern formed by using the curable resin composition tends to be improved. desirable.

Curable resin composition of this invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of the curable resin composition, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl. Ethylene glycol monoalkyl ethers such as ether;

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

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;

Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether

Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;

Butyl diol monoalkyl ethers such as methoxy butyl alcohol, ethoxy butyl alcohol, propoxy butyl alcohol and butoxy butyl alcohol;

Butanediol monoalkyl ether acetates, such as a methoxy butyl acetate, an ethoxy butyl acetate, a propoxy butyl acetate, butoxy butyl acetate;

Butanediol monoalkyl ether propionate, such as a methoxy butyl propionate, an ethoxy butyl propionate, a propoxy butyl propionate, butoxy butyl propionate;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetic acid, hydroxyacetic acid Ethyl, butyl hydroxy acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionate propyl, 3-hydroxypropionate butyl, 2-hydroxy Methyl oxy-3-methyl butyrate, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate propyl, butyl acetate, ethoxy acetate methyl, ethoxy acetate, ethoxy acetate propyl, butyl ethoxy acetate, pro Methyl acetate, ethyl propoxy acetate, propyl acetate, propoxy acetate, butyl acetate, methyl butoxy acetate, ethyl butoxy acetate, Propyl acetate, butyl butoxy acetate, methyl 2-methoxypropionate, 2-methoxy ethylpropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Methyl propoxypropionate, 3-propoxy propionate, 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid Esters such as ropil, 3-butoxy-propionic acid butyl;

Cyclic ether groups such as tetrahydrofuran and pyran;

Cyclic ester, such as (gamma) -butyrolactone, etc. are mentioned.

Among the above solvents, in view of applicability, printability, solubility and dryness, ester solvents, ether solvents and alcohol solvents having a boiling point of 200 ° C or higher, preferably 200 to 300 ° C are preferable.

An ester solvent means the organic solvent which has an ester bond and does not have a hydroxyl group.

As a specific example of an ester solvent, it is diethylene glycol monoethyl ether acetate (boiling point 217 degreeC), diethylene glycol monopropyl ether acetate (232 degreeC), diethylene glycol monobutyl ether acetate (boiling point 247 degreeC), Glycerin triacetate (boiling point of 260 degreeC) is mentioned, Preferably, diethylene glycol monobutyl ether acetate (boiling point of 247 degreeC) and glycerine triacetate (boiling point of 260 degreeC) are mentioned.

An ether solvent means an organic solvent which has an ether bond and does not have an ester bond and a hydroxyl group.

As a specific example of the said ether solvent, it is a diethylene glycol butyl methyl ether (boiling point 212 degreeC), tripropylene glycol dimethyl ether (boiling point 215 degreeC), triethylene glycol dimethyl ether (boiling point 216 degreeC), diethylene glycol, for example. Dibutyl ether (boiling point 256 degreeC), triethylene glycol butyl methyl ether (boiling point 261 degreeC), and tetraethylene glycol dimethyl ether (boiling point 275 degreeC) are mentioned, Preferably diethylene glycol dibutyl ether (boiling point 256 degreeC) is mentioned. And triethylene glycol butyl methyl ether (boiling point 261 ° C.).

An alcoholic solvent means the organic solvent which has a hydroxyl group.

As an example of the said alcohol solvent, For example, ethylene glycol monohexyl ether (boiling point 208 degreeC), ethylene glycol mono 2-ethylhexyl ether (boiling point 229 degreeC), ethylene glycol monophenyl ether (boiling point 245 degreeC), Ethylene glycol monobenzyl ether (boiling point 256 ° C), diethylene glycol monoisopropyl ether (boiling point 207 ° C), diethylene glycol monoisobutyl ether (boiling point 220 ° C), diethylene glycol monobutyl ether (boiling point 230 ° C), di Ethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point 259 ° C), diethylene glycol mono2-ethylhexyl ether (272 ° C), diethylene glycol monophenyl ether (boiling point 283 ° C), triethylene glycol monomethyl ether (Boiling point 249 ° C), triethylene glycol monobutyl ether (boiling point 271 ° C), polyethylene glycol monomethyl ether (boiling point 295 ° C), tripropylene glycol monomethyl ether (boiling point 242 ° C), dipropyl Len glycol monopropyl ether (boiling point 212 degreeC), dipropylene glycol monobutyl ether (boiling point 231 degreeC), and propylene glycol monophenyl ether (boiling point 243 degreeC) are mentioned, Preferably ethylene glycol monophenyl ether (boiling point 245 degreeC) is mentioned. ), Ethylene glycol monobenzyl ether (boiling point 256 ° C.), diethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point 259 ° C.), and propylene glycol monophenyl ether (boiling point 243 ° C.).

These solvents (D) may be used independently, respectively and may be used in mixture of 2 or more types.

In curable resin composition of this invention, the quantity of the solvent (D) with respect to the total amount of binder resin (A), a polymeric compound (B), and a solvent (D) is 20 mass% or more and less than 60 mass% by mass fraction, for example. Preferably they are 20 mass% or more and less than 50 mass%, More preferably, they are 25 mass% or more and 50 mass% or less. When content of a solvent (D) is less than 20 mass%, since the viscosity of a curable composition becomes high too much, the transferability in the printing method will become inferior. On the other hand, when it becomes 80 mass% or more, since the viscosity of a curable composition becomes too low, since a curable composition remains well in a recessed plate, it becomes difficult to apply to a printing method.

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, content of the coloring agent with respect to the whole composition is less than 1 mass%, Preferably it is less than 0.5 mass% by mass fraction, for example.

For example, the curable resin composition of this invention does not contain the following coloring agents substantially used in the field | area.

Compounds classified as Pigments in the Color Index (published by The Society of Dyers and Colourists), specifically,

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214;

C.I. Pigment oranges such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ;

C.I. Blue pigments such as Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60;

C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments such as pigment green 7, 36;

C.I. Brown pigments such as pigment brown 23 and 25;

C.I. Black pigments, such as pigment black 1 and 7.

The curable resin composition of this invention can also use together additives, such as a filler, another high molecular compound, a leveling agent, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, an aggregation inhibitor, a chain transfer agent, as needed.

Specific examples of the filler include glass, silica, alumina, and the like.

Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, and polyurethanes. Can be.

As the leveling agent, commercially available surfactants can be used, and for example, surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, etc. may be used. You may use in combination of 2 or more type. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Material Electronic Chemicals Co., Ltd.), Megapack (DIC ( Manufacture), Furard (manufactured by Sumitomo 3M), Asahi Guard (manufactured by Asahi Glass Lee, Inc.), Saffron (manufactured by AGC Seimi Chemical Co., Ltd.), Solsperth (manufactured by Geneca Co., Ltd.) And EFKA (manufactured by CIBA), Ajispa PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As an adhesion promoter, a silane type compound is preferable, Specifically, a vinyl trimethoxysilane, a vinyl triethoxysilane, a vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Methoxysilane, 3-mercaptopropyltrimethoxysilane, etc. are mentioned.

Specific examples of antioxidants include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3 , 5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl -4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10- tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6- tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol ), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'- thiodipropionate, dimyristyl 3,3'- thiodipropionate, dis Tearyl 3,3'- thiodipropionate, pentaerythryl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-part -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 the like.

Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole and octyl-3- [3-tert-butyl-4-hydroxy-5- (5- Chloro-2H-benzotriazol-2-yl) phenyl] propionate, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl ] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4- Bis-butyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole- 2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert-butyl-2-hydroxy-5 -Methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. are mentioned.

Specifically as a light stabilizer, a polymer consisting of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ', N' ', N' ' '-Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin-2-yl) -4,7- Diazadecane-1,10-diamine, decandioic acid and bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and 1,1-dimethylethylhydro Reactant of peroxide, bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] Methyl] butylmalonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- ( 2-hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6 , 6-pentamethyl-4-piperidinyl) sebacate and the like.

Examples of the aggregation prevention material include sodium polyacrylate.

Moreover, dodecyl mercaptan, 2, 4- diphenyl-4-methyl-1- pentene etc. are mentioned as a chain transfer agent.

Since curable resin composition of this invention is low in dryness, it is hard to produce the dry foreign material by volatilization of a solvent, and it is especially suitable for the printing method, because storage stability is good even in high solid content.

The printing method may be applied to a printing method known in the art, for example, an inkjet printing method, a flexographic printing method, a gravure printing method, an offset printing method, a screen printing method, or the like.

Moreover, when curable resin composition of this invention is filled into the quartz cell whose optical path length is 1 cm, and transmittance | permeability is measured on the conditions of 400-700 nm of measurement wavelengths using a spectrophotometer, average transmittance is 70% or more, Preferably it is Is 75% or more. Thereby, a transparent pattern and a coating film can be formed.

Although the hardening conditions of curable resin composition of this invention are suitably selected according to the kind, content, etc. of each component of a composition, it is the heat hardening using the photocuring using an ultraviolet-ray etc., an oven, etc. normally.

Moreover, the curable resin composition of this invention uses the spectrophotometer with respect to the coating film of 3 micrometer thickness after heat-hardening (for example, 150-250 degreeC, 0.1 to 3 hours), The conditions of measurement wavelength 400-700 nm. When the transmittance is measured under, the transmittance is 90% or more, and preferably 95% or more. Thereby, a transparent pattern and a coating film can be formed.

The curable resin composition of this invention is apply | coated by the printing method on the base material which formed the glass substrate, the film substrate, the color filter, or the drive circuit as follows, for example, photocuring or heat-hardening, and a coating film Or you can form a pattern.

First, this curable resin composition is apply | coated by the printing method on the board | substrate (usually glass) or the layer which consists of solid content of the curable resin composition already formed, and prebaked from the apply | coated curable resin composition layer, volatile components, such as a solvent, are It removes and obtains a smooth uncured coating film (including a pattern). The thickness of the uncured coating film at this time is about 1-6 micrometers. The uncured coating film thus obtained may be irradiated with ultraviolet rays generated from a mercury lamp or a light emitting diode.

Moreover, in pattern formation, the line width can be suitably controlled by the recess plate size.

Moreover, you may perform the post-baking for 10 to 180 minutes at 150-230 degreeC as needed.

Using the curable resin composition of this invention, a coating film or a pattern can be formed on a board | substrate or a color filter substrate through each process as mentioned above. This coating film or pattern is useful as a photo spacer used for a liquid crystal display device, a projection for liquid crystal alignment, a partition, and an overcoat.

By attaching the coating film and pattern obtained in this way to display apparatuses, such as a liquid crystal display device, a display apparatus of excellent quality can be manufactured with a high yield.

Example

EXAMPLES Hereinafter, although an Example demonstrates this in more detail, it cannot be overemphasized that this invention is not limited by these Examples. In the examples,% and parts representing the content to the amount used are based on mass unless otherwise specified.

Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto and heated to 70 ° C while stirring. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1), mol) 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution is added to the dropwise pump in 4 hours. It dripped over the flask heated over 70 degreeC over. On the other hand, a solution in which 45 parts by mass of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to the flask over 5 hours using another dropping pump. It dripped. After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a resin solution of a copolymer having a solid content of 32.6 mass% and an acid value of 34.3 mg-KOH / g. The weight average molecular weight Mw of obtained resin Aa was 9,000, and dispersion degree was 2.01. 45 mass parts of diethylene glycol n-butyl ether acetates were put into 245 mass parts of this resin solutions, and 3-methoxybutyl acetate was concentrated and distilled off at 90 degreeC under reduced pressure using a rotary evaporator, and solid content 64.0 mass A diethylene glycol n-butyl ether acetate solution of% resin Aa was obtained. The acid value, weight average molecular weight Mw and dispersion degree were equivalent to before concentration.

Synthesis Example 2

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto and heated to 70 ° C while stirring. Next, 60 parts by mass of methacrylic acid, 3,4-epoxycitcyclo [5.2.1.0 ^2,6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) are molar) The mixture was dissolved in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution. The solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. It was. Meanwhile, a solution in which 45 parts by mass of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to the flask over 4 hours using another dropping funnel. It dripped. 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 resin solution of the copolymer of 32.3 mass% of solid content, and the acid value 35.6 mg-KOH / g. The weight average molecular weight Mw of obtained resin Ab was 9,100, and dispersion degree was 2.02. 45 mass parts of diethylene glycol n-butyl ether acetates were put into 245 mass parts of this resin solutions, and 3-methoxybutyl acetate was concentrated and distilled off at 90 degreeC under reduced pressure using a rotary evaporator, and solid content 64.0 mass A diethylene glycol n-butyl ether acetate solution of% resin Re was obtained. The acid value weight average molecular weight Mw and the degree of dispersion were equivalent to before concentration.

(Measurement of molecular weight)

About the measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin Aa and Ab, it carried out on condition of the following using GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

Example 1

40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) to 2-part (60 parts of solid content conversion) of the resin solution containing resin Aa obtained by the synthesis example 1, 2-methyl-2- morpholi 1 part of no-1- (4-methylsulfanylphenyl) propan-1-one and 34 parts of diethylene glycol n-butyl ether acetates were mixed so that curable resin composition 1 was obtained.

Next, the pattern was formed from curable resin composition 1 as follows. The method will be described with reference to FIG. 1.

First, curable resin composition 1 (2) was dripped from the supply apparatus 1 on the recessed plate 3 set to the experimental printing machine (process a). The remaining curable resin composition 1 was scraped off with the scraper blade 5 while the dropped curable resin composition 1 was evenly fed with the feed blade 4 (step b). Next, the transfer body 7 having the transfer sheet 6 mounted on the outer circumferential surface was rolled onto the recess plate 3 to transfer the curable resin composition 1 to the transfer sheet 6 surface (step c). Next, the curable resin composition 1 of the transfer sheet 6 surface was transferred to the base material 8 surface (step d).

After transferring to the base material 8, it dried by 100 degreeC / 10 minutes, heat-hardened by exposure 100mJ / cm <2> (I line | wire), and 220 degreeC / 20 minutes, and obtained the pattern 1.

[Example 2]

In Example 1, except having abbreviate | omitted the exposure process, operation similar to Example 1 was performed and the pattern 2 was obtained from curable resin composition 1.

Example 3

Curable resin composition 2 and the pattern 3 were obtained like Example 1 so that it might become the composition shown in Table 1.

Example 4

Curable resin composition 3 and the pattern 4 were obtained like Example 1 so that it might become the composition shown in Table 1.

Example 5

Curable resin composition 4 and the pattern 5 were obtained like Example 1 so that it might become the composition shown in Table 1.

Comparative Example 1

Curable resin composition 5 was obtained like Example 1 so that it might become a composition shown in Table 1. When curable resin composition 5 used the printing method similarly to Example 1, since a large amount of curable composition remained in the recessed plate, the pattern could not be formed.

The following evaluation was performed about the curable resin compositions 1-5 and patterns 1-6 obtained as mentioned above. The results are shown in Table 1.

<Average transmittance of composition>

Average transmittance (%) in 400-700 nm using an ultraviolet-visible near-infrared spectrophotometer (V-650; Nippon Spectroscopy Co., Ltd. product) (quartz cell, optical path length; 1 cm) with respect to each curable resin composition. ) Was measured.

<Mean Transmittance of Membrane>

Using each curable resin composition, the cured film was produced as follows so that the film thickness after hardening might be set to 3 micrometers.

The curable resin composition was diluted with diethylene glycol n-butyl ether acetate so that solid content might be 20 mass%. It applied by the spin coating method so that the film thickness might be set to 3 micrometers, and after 100 degreeC x 10 minute prebaking, it heat-hardened at 220 degreeC x 20 minutes.

About each obtained cured film, the average transmittance (%) in 400-700 nm was measured using the microscopic spectrophotometer (OSP-SP200; OLYMPUS company make).

Higher transmittance means less absorption.

<Shape of pattern>

The shape of each pattern was measured by the three-dimensional non-contact surface shape measuring system (made by Micromap MM527N Ryoka System).

From the result of Examples 1-5 shown in Table 1, it turns out that the curable resin composition of this invention containing a predetermined amount of solvent can form the coating film and pattern of high transmittance | permeability using the printing method. On the other hand, in Comparative Example 1, the printing method could not be used.

Curable resin composition of this invention can form the coating film and pattern excellent in the transmittance | permeability using the printing method. Therefore, it can use suitably for formation of the coating film and pattern used for a display apparatus, such as an overcoat, a photo spacer, an insulating film, the processus | protrusion for liquid crystal orientation control, and the coating layer for matching the film thickness of a coloring pattern.

1 shows a method of forming a pattern from a resin composition using a printing method.

[Description of Reference Numerals]

1 feeder

2 resin composition

3 intaglio

4 feeding blade

5 scraper blade

6 transfer sheet

7 warrior fuselage

8 description

Claims (16)

Binder resin (A), a polymeric compound (B), and a solvent (D) are contained, Curable resin composition whose amount of solvent (D) with respect to the total amount of binder resin (A), a polymeric compound (B), and a solvent (D) is 20 mass% or more and less than 60 mass%. The method of claim 1, Curable resin composition whose quantity of solvent (D) with respect to the total amount of binder resin (A), a polymeric compound (B), and a solvent (D) is 25 mass% or more and 50 mass% or less. The method according to claim 1 or 2, The binder resin (A) polymerizes at least one compound (Aa) selected from the group consisting of at least unsaturated carboxylic acid and unsaturated carboxylic anhydride, and a monomer (Ac) having a cyclic ether structure having 2 to 4 carbon atoms. Curable resin composition which is a copolymer formed by making. The method of claim 3, wherein Curable resin composition whose monomer (A-c) which has a C2-C4 cyclic ether structure is a monomer which has an epoxy group. The method of claim 4, wherein Curable resin composition whose monomer which has an epoxy group is a monomer which has an aliphatic polycyclic epoxy group. The method of claim 5, Curable resin composition whose monomer which has an aliphatic polycyclic epoxy group is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II).

[In formula (I) and formula (II), R <_1> and R <_2> represents a hydrogen atom or a C1-C4 alkyl group each independently. The hydrogen atom contained in this alkyl group may be substituted by the hydroxy group. X ₁ and X ₂ each independently represent a C 1-6 alkylene group which may contain a single bond or a hetero atom; The method according to any one of claims 3 to 6, Curable at least one compound (Aa) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides is at least one compound selected from the group consisting of aliphatic unsaturated carboxylic acids and aliphatic unsaturated carboxylic anhydrides Resin composition. The method of claim 6, At least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) is selected from the group consisting of a compound represented by formula (I ') and a compound represented by formula (II') Curable resin composition which is at least 1 sort (s) of compound.

In formula (I ') and formula (II'), R <_1>'and R <_2>' respectively independently represent a hydrogen atom or a C1-C4 alkyl group. The hydrogen atom contained in this alkyl group may be substituted by the hydroxy group] 9. The method according to any one of claims 1 to 8, Curable resin composition whose solvent (D) is a solvent which has a boiling point of 200 degreeC or more and contains at least 1 sort (s) of solvent chosen from the group which consists of ester solvent, ether solvent, and alcohol solvent. The method according to any one of claims 1 to 9, Curable resin composition containing a polymerization initiator (C) further. The method of claim 10, Curable resin (C) which is a polymerization initiator containing at least 1 sort (s) of compound chosen from the group which consists of a biimidazole type compound, an acetophenone type compound, a triazine type compound, an acylphosphine oxide type compound, and an oxime type compound. Composition. Use of curable resin composition in any one of Claims 1-11 for forming a coating film or a pattern. The coating film or pattern formed using the curable resin composition of any one of Claims 1-11. The display device containing the coating film or pattern of Claim 13. The manufacturing method of the coating film or pattern which has the process of apply | coating curable resin composition of any one of Claims 1-11 on a base material using a printing method, drying, and heating to obtain a coating film or a pattern. The curable resin composition of any one of Claims 1-11 is apply | coated on a base material using a printing method, it has a process of drying, exposing, heating as needed, and obtaining a coating film or a pattern as needed. Method of producing a coating film or pattern.

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