TWI464189B - Hardened resin composition - Google Patents

Description

Curable resin composition

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

At present, a liquid crystal display device, a touch panel, or the like is formed between a color filter constituting a display device and an array substrate, and a spacer (lithographic spacer) is formed by photolithography using a photosensitive resin. . By this method, a spacer can be formed at any place. A photosensitive resin composition containing a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent is known as a composition for photolithography (Patent Document 1).

However, such photolithography is a pattern of spacers formed by steps of film formation, exposure, development, etc., the steps are long and complicated, and large-scale manufacturing equipment is necessary.

A method other than photolithography is known in which a liquid ink containing a curable resin composition is applied to a printed substrate by a printing method such as an inkjet printing method or a flexographic printing method. A method of forming a pattern by a specific position on a material (Patent Document 2).

[Patent Document 1] JP-A-2006-171160

[Patent Document 2] JP-A-2008-158284

However, the amount of the solvent contained in the photosensitive resin composition described in Patent Document 1 is 60% by mass or more based on the total composition, and the amount of the solvent contained in the curable resin composition described in Patent Document 2 is relative to the total composition. When it is 80% by mass or more, it takes a long time to remove the solvent after printing, and it is not easy to use in the printing method because of shape change after printing or drying.

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

The inventors of the present invention have found that the amount of the solvent to be contained is 20% by mass or more and less than 60% by mass based on the total composition, in order to find a result of the curable resin composition which can solve the above-mentioned problems. The present invention has been completed by a printing method to obtain a curable resin composition which can form a coating film or a pattern having a high transmittance.

That is, the present invention provides the following [1] to [16].

[1] A curable resin composition comprising a binder resin (A), a polymerizable compound (B), and a solvent (D), with respect to a binder resin (A), a polymerizable compound (B), and a solvent (D) The total amount of the solvent (D) is 20% by mass or more and less than 60% by mass.

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

[3] The curable resin composition according to the above [1] or [2] wherein the binder resin (A) is at least at least selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa). A copolymer obtained by polymerizing a compound and a monomer (Ac) having a cyclic ether having 2 to 4 carbon atoms.

[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 selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II). A group of at least one compound.

In the formulae (I) and (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ₁ and X ₂ each independently represent an alkylene group having 1 to 6 carbon atoms which may have a single bond or a hetero atom. ]

[7] The curable resin composition according to any one of the above [3], wherein at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa) is selected from the group consisting of at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (Aa). A compound of at least one of a group consisting of an aliphatic unsaturated carboxylic acid and an aliphatic unsaturated carboxylic anhydride.

[8] The curable resin composition according to the above [6], wherein at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) is selected from the formula ( At least one compound of the compound represented by I') and the compound represented by the formula (II').

[In the formula (I') and the formula (II'), R ₁ ' and R ₂ ' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. ]

[9] The curable resin composition according to any one of the above [1], wherein the solvent (D) has a boiling point of 200 ° C or higher and contains an ester solvent, an ether solvent, and an alcohol solvent. A solvent of at least one solvent of the group.

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

[11] The curable resin composition according to the above [10], wherein the polymerization initiator (C) contains a compound selected from the group consisting of a bisimidazole compound, an acetophenone compound, a triazine compound, and a mercaptophosphine oxide compound. And a polymerization initiator for at least one compound of the group of the lanthanoid compounds.

[12] The use of the curable resin composition according to any one of the above [1] to [11], which is to form a coating film or a pattern.

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

[14] A display device comprising the coating film or pattern described in the above [13].

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

[16] A method for producing a coating film or a pattern, comprising applying the curable resin composition according to any one of the above [1] to [11] on a substrate by a printing method, and drying the composition. The exposure treatment and the step of heating to obtain a coating film or a pattern are required.

Effect of invention

The curable resin composition of the present invention can form a coating film or pattern having a high transmittance by a printing method.

Hereinafter, the present invention will be described in detail.

The curable resin composition of the present invention contains the binder resin (A), the polymerizable compound (B), and the solvent (D), and the total amount of the binder resin (A) relative to the polymerizable compound (B) and the solvent (D) The amount of the solvent (D) is 20% by mass or more and less than 60% by mass.

The binder resin (A) used for the curable resin composition of the present invention may, for example, be a binder resin (A1) or a binder resin (A2). The binder resin (A1) has an acidic group, and the binder resin (A2) has an acidic group and exhibits reactivity by at least one of light and heat.

When the binder resin has an acidic group, the Tg of the binder resin and the mechanical properties tend to be high. In addition, when the monomer (A-c) having a cyclic ether structural group having 2 to 4 carbon atoms is contained as a copolymer component, it is preferred that the curing property is increased, and chemical resistance and heat resistance are increased.

The binder resin (A1) is exemplified by at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Aa) (hereinafter referred to as "(Aa)"), and may be co-produced with (Aa) A copolymer of a monomer (Ab) (other than (Aa)) (hereinafter referred to as "Ab").

(Aa), for example, an aliphatic unsaturated carboxylic acid and/or an aliphatic unsaturated carboxylic anhydride, and the like, and specific examples thereof include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; An unsaturated carboxylic acid such as acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; and an anhydrous of the aforementioned unsaturated dicarboxylic acid; succinic acid mono [2-(methyl) propylene hydride Unsaturated mono[(methyl)acryloxyalkylene group of a polyvalent carboxylic acid having two or more valences such as oxyethyl] ester and decanoic acid mono [2-(methyl) propylene methoxyethyl] ester An ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among them, acrylic acid, methacrylic acid or anhydrous maleic acid is preferred because it has good copolymerization reactivity, high Tg and mechanical properties of the copolymer, and no tack property. These can be used singly or in combination.

(Ab), methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-(meth)acrylate Alkyl (meth)acrylates such as butyl ester; cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo(methyl)acrylate [5.2.1.0 ^{2, 6} ]decane-8-yl ester (common name in the art is called Dicyclopentanyl Methacrylate), dicyclopentyloxyethyl (meth)acrylate (meth)acrylic cyclic alkyl esters such as esters, isophoryl (meth)acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclohexyl acrylate [5.2.1.0 ^2,6 a decane-8-yl ester (common name in the art is called dicyclopentyl acrylate), an acrylic cyclic alkyl group such as dicyclopentyloxyethyl acrylate or isophoryl acrylate. Esters; (meth)acrylic acid aromatic esters such as phenyl (meth) acrylate, benzyl (meth) acrylate; acrylic aryl esters such as phenyl acrylate and benzyl acrylate; diethyl maleate, Fumaric acid a dicarboxylic acid diester such as ethyl ester or diethyl itaconate; a hydroxyalkyl ester such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; bicyclo[2.2 .1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1] Hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxymethyl)bicyclo[ 2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxyl Bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2- Alkene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6 -diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1 Hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxyl Methyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2 .1 Hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride (humic anhydride), 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-di(tert-butoxycarbonyl) a bicyclic unsaturated compound such as bicyclo [2.2.1] hept-2-ene, 5,6-di(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl mala Imine, N-cyclohexylmaleimide, N-benzylmaleimide, N-butylenediamine-3-maleimide benzoate, N-butadiene Amino-4-maleimide butyrate, N-butylenediamine-6-maleimide hexanoate, N-butylenediamine-3-maleimide Dicarbonyl quinone imine derivatives such as propionate, N-(9-acridinyl)maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Alkene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene The viewpoint of copolymerization reactivity and alkali solubility is preferred.

(A-a) and (A-b) may be used singly or in combination.

In the present specification, (meth) acrylate means acrylate and/or methacrylate.

In the copolymer obtained by copolymerizing (Aa) and (Ab), the ratio of the constituent components derived from the respective copolymers is such that the total number of moles of the constituent components constituting the copolymer is 100 mol%. The molar fraction is preferably in the range below.

Constituent units derived from (A-a): 2~40 mol%

The constituent units derived from (A-b): 60~98 mol%

Further, the ratio of the above-mentioned constituent components is more preferably in the following range.

Constituent units derived from (A-a): 5~35 mol%

Constituent units derived from (A-b): 65~95 mol%

When the composition ratio is within the above range, the storage stability and the solvent resistance tend to be good.

The binder resin (Al) can be referred to, for example, the method described in the literature "Experimental method for polymer synthesis" (Dazu Takashi, Institute of Chemicals, 1st edition, 1st brush, issued on March 1, 1972) and the document. The cited documents are manufactured.

Specifically, a predetermined amount, a polymerization initiator, and a solvent of the units (Aa) and (Ab) constituting the copolymer are placed in a reaction vessel, and oxygen is replaced by nitrogen, and stirring is carried out in the absence of oxygen. The polymer is obtained by heating and keeping warm. Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution obtained by concentration or dilution thereof, or a solid (powder) taken out by a method such as re-sinking.

The weight average molecular weight of the binder resin (A1) in terms of polyethylene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) having an acidic group is in the above range, the coating property tends to be good, and the Tg and mechanical properties of the binder resin tend to be high, and the adhesiveness tends to be insufficient. Therefore, it is better.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A1) is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the coating property tends to be excellent, which is preferable.

The content of the binder resin (A1) to be used in the curable resin composition of the present invention is preferably 5 to 90% by mass, more preferably 10%, based on the solid content of the curable resin composition. ~70% by mass. When the content of the binder resin (A1) is within the above range, the printability tends to be good, which is preferable.

The binder resin (A2) which has an acidic group and exhibits reactivity by the action of either light or heat can be exemplified by (A2-1) to (A2-3).

Copolymer resin (A2-1) is a copolymer of (Aa) and (Ab) and a monomer (Ac) having a cyclic ether structure of 2 to 4 (hereinafter referred to as "Ac"). Things.

The binder resin (A2-2) is a copolymer of (Aa) and (Ab) by using a part of the carboxyl group derived from (Aa) and a cyclic ether derived from (Ac) having 2 to 4 carbon atoms. The copolymer obtained by the reaction was constructed.

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

(Ac) is, for example, a polymerizable compound having at least one structure selected from the group consisting of a cyclic ether structure having 2 to 4 carbon atoms (for example, an ethylene oxide structure, an oxycyclobutane 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 a cyclic ether structure having 2 to 4 carbon atoms and having a carbon-carbon unsaturated bond. The compound is preferably a compound having at least one structure selected from the group consisting of a cyclic ether structure having 2 to 4 carbon atoms and having a propylene fluorenyl group or a methacryl fluorenyl group.

(A-c), for example, a monomer having an epoxy group, a monomer having an oxycyclobutane group, a monomer having a tetrahydroindenyl group, and the like can be given.

The single system having an epoxy group as described above means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group. The single system having an epoxy group is preferably a compound having at least one selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group, and having a carbon-carbon unsaturated bond. A compound having a structure selected from at least one selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group, and having a propylene fluorenyl group or a methacryl fluorenyl group is preferred.

Here, the aliphatic epoxy group means a monocyclic oxiranyl group, and the alicyclic epoxy group means a group having a structure in which a ring of an alicyclic hydrocarbon is condensed with an oxirane ring.

Among the above-mentioned monomers having an epoxy group, the compound having an aliphatic epoxy group may specifically be a glycidyl (meth) acrylate, a β-methyl propyl propyl (meth) acrylate, or a β. - Ethyl propyl propyl (meth) acrylate, a propylene propyl acrylate, and a compound represented by the following formula, which are described in JP-A-H07-248625.

(wherein R ¹¹ to R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m is an integer of 1 to 5).

Examples of the compound represented by the above formula include o-vinylbenzylepoxypropyl ether, m-vinylbenzylepoxypropyl ether, p-vinylbenzylepoxypropyl ether, and α-methyl-o. -vinylbenzylepoxypropyl ether, α-methyl-m-vinylbenzylepoxypropyl ether, α-methyl-p-vinylbenzylepoxypropyl ether, 2,3-diepoxypropyl Hydroxymethylstyrene, 2,4-diepoxypropyloxymethylstyrene, 2,5-diepoxypropyloxymethylstyrene, 2,6-diepoxypropyloxy Methylstyrene, 2,3,4-triepoxypropyloxymethylstyrene, 2,3,5-triepoxypropyloxymethylstyrene, 2,3,6-tricyclic Oloxypropyloxymethylstyrene, 3,4,5-triepoxypropyloxymethylstyrene, 2,4,6-triepoxypropyloxymethylstyrene, and the like.

Among the above-mentioned monomers having an epoxy group, the monomer having an alicyclic epoxy group may, for example, be a monomer having an aliphatic monocyclic epoxy group or a single having an aliphatic polycyclic epoxy group. Body and so on.

The above-mentioned single system having an aliphatic monocyclic epoxy group means a polymerizable compound having a structure in which a ring of a monocyclic alicyclic hydrocarbon is condensed with an oxirane ring. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having a monocyclic alicyclic hydrocarbon ring condensed with an oxirane ring, and a compound having a carbon-carbon unsaturated bond is preferred. A compound having a monocyclic alicyclic hydrocarbon ring condensed with an oxirane ring and having a propylene fluorenyl group or a methacryl fluorenyl group is more preferable.

Examples of the ring of the monocyclic alicyclic hydrocarbon include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. Among them, a ring having 4 to 6 carbon atoms is preferred.

The monomer having an aliphatic monocyclic epoxy group, specifically, ethylenecyclohexene monooxide 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Daicel Chemical Industry Co., Ltd. ), 3,4-epoxycyclohexyl methacrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100; Daicel Chemical Industry Co., Ltd.).

The above-mentioned single system having an aliphatic polycyclic epoxy group means a polymerizable compound having a structure in which a ring of an alicyclic hydrocarbon having a polycyclic ring is condensed with an oxirane ring. The monomer having a structure in which a ring of a polycyclic alicyclic hydrocarbon is condensed with an oxirane ring has a structure in which a ring having a polycyclic alicyclic hydrocarbon is condensed with an oxirane ring, and has a carbon- The carbon-unsaturated bonded compound is preferred, and a compound having a polycyclic alicyclic hydrocarbon ring condensed with an oxirane ring and having a propylene fluorenyl group or a methacryl fluorenyl group is more preferable.

Examples of the ring of the polycyclic alicyclic hydrocarbon include a dicyclopentane ring, a tricyclodecane ring, a norbornane ring, an isodecane ring, a bicyclooctane ring, a bicyclodecane ring, and a bicyclo 11 An alkane ring, a tricycloundecane ring, a bicyclododecan ring, a tricyclododecane ring or the like, wherein a compound having 8 to 12 carbon atoms is preferred.

The monomer having an aliphatic polycyclic epoxy group is, for example, a compound selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II).

In the formulae (I) and (II), R ₁ and R ₂ each independently represent an alkyl group having 1 to 4 carbon atoms which may be substituted by a hydrogen atom or a hydroxyl group.

X ₁ and X ₂ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a hetero atom.

Specific examples of R ₁ and R ₂ include a hydrogen atom; an alkyl group of a methyl group, an ethyl group, an N-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, or the like; a hydroxymethyl group; , 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1-hydroxy-isopropyl, 2- A hydroxy-containing alkyl group such as hydroxy-isopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl or the like. Among them, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydrogen atom or a methyl group is more preferable.

Specific examples of X ₁ and X ₂ include a single bond; an alkylene group such as a methylene group, an ethyl group, and a propyl group; an oxymethylene group, an oxyethyl group, an oxypropyl group, and a thiomethylene group; And a thiol-ethyl group, a thio-propyl group, an aminomethylene group, an amine group ethyl group, an amine group propyl group, and the like, and a hetero atom-containing alkyl group. Among them, a single bond, a methylene group, an ethylidene group, an oxymethylene group, and an oxyethyl group are preferable, and a single bond or an oxyethyl group is more preferable.

The compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II), which is selected from the group consisting of the compound represented by the following formula (I') and the formula (II') It is preferred that at least one of the compounds represented by the group is a compound.

In the formula (I') and the formula (II'), R ₁ ' and R ₂ ' are each synonymous with the above R ₁ and R ₂ .

Specific examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to the formula (I-15), and the formula (I-1) and the formula (I-3) are preferred. ), formula (I-5), formula (I-7), formula (I-9), formula (I-11) to formula (I-15), more preferably formula (I-1), formula (I-7), formula (I-9), and formula (I-15).

Specific examples of the compound represented by the formula (II) include a compound represented by the formula (II-1) to the formula (II-15), and preferably a formula (II-1) or a formula (II-3). , formula (II-5), formula (II-7), formula (II-9), formula (II-11) to formula (II-15), more preferably formula (II-1), formula ( II-7), formula (II-9), formula (II-15).

At least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in any ratio. In the case of mixing, the mixing ratio is preferably in the molar ratio (I): formula (II) is from 5:95 to 95:5, preferably from 10:90 to 90:10, more preferably from 20:80. 80:20.

The above-mentioned single system having an oxycyclobutane group means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxycyclobutane group and an alicyclic oxycyclobutane group. The single system having an oxycyclobutane group has at least one selected from the group consisting of an aliphatic oxycyclobutane group and an alicyclic oxocyclobutane group, and the compound having an unsaturated bond is good.

Specific examples of the monomer having an oxycyclobutane group include 3-methyl-3-methylpropenyloxymethyloxycyclobutane and 3-methyl-3-propenyloxymethyloxycyclobutane. Alkane, 3-ethyl-3-methylpropenyloxymethyloxycyclobutane, 3-ethyl-3-propenyloxymethyloxycyclobutane, 3-methyl-3-methylpropene Ethoxyethyloxycyclobutane, 3-methyl-3-propenyloxyethyloxycyclobutane, 3-ethyl-3-methylpropenyloxyethyloxycyclobutane or 3- Ethyl-3-propenyloxyethyloxycyclobutane or the like.

These can be used singly or in combination.

The above-mentioned single system having a tetrahydroindenyl group means, for example, a polymerizable compound having at least a group selected from the group consisting of an aliphatic tetrahydroindenyl group and an alicyclic tetrahydroindenyl group. The single system having a tetrahydroindenyl group is preferably a compound having at least one selected from the group consisting of an aliphatic tetrahydroindenyl group and an alicyclic tetrahydroindenyl group, and having an unsaturated bond.

Specific examples of the monomer having a tetrahydroindenyl group include tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate.

These may be used singly or in combination.

In the binder resin (A2-1), the ratio of the constituent components derived from each of the components is expressed in the following range with respect to the total number of moles of the constituent components constituting the binder resin (A2-1). It is better.

Constituent units derived from (A-a): 2~40 mol%

Constituent units derived from (A-b): 1~65mol%

Constituent units derived from (A-c): 2~95 mol%

Further, the ratio of the aforementioned constituent components is more preferably in the range below.

Constituent units derived from (A-a): 5~35 mol%

Constituent units derived from (A-b): 1~60 mol%

The constituent units derived from (A-c): 5~80 mol%

When the composition ratio is within the above range, the stability, the solvent resistance, the heat resistance, and the mechanical strength tend to be good.

The binder resin (A2-1) can be referred to, for example, the method described in the literature "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). The cited documents described in the literature are manufactured.

Specifically, the compounds derived from the units (Aa), (Ab), and (Ac) constituting the copolymer can be metered in a predetermined amount, a polymerization initiator, and a solvent, and the oxygen is substituted in the absence of oxygen. The polymer was obtained by stirring, heating, and heat preservation. Further, the obtained copolymer may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) may be used by a method such as re-sinking.

When the binder resin (A2-2) is produced, (A-a) and (A-b) are first copolymerized to produce a copolymer. The ratio of the constituent components derived from each of the components is preferably in the range of the following with respect to the total number of moles constituting the constituent components of the copolymer.

Constituent units derived from (A-a): 5~50 mol%

Constituent units derived from (A-b): 50~95 mol%

Further, the ratio of the above-mentioned constituent components is more preferably in the following range.

The constituent units derived from (A-a): 10~45 mol%

Constituent units derived from (A-b): 55~90 mol%

Next, in order to have reactivity due to the action of light or heat, a part of the carboxylic acid and the carboxylic anhydride derived from the copolymer obtained by copolymerizing (Aa) and (Ab) is derived from (Ac) an epoxy group or an oxocyclobutane group.

The number of moles of (A-c) is from 5 to 80 mol%, preferably from 10 to 75 mol%, more preferably from 15 to 70 mol%, relative to the number of moles of (A-a).

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

The binder resin (A2-2) can be produced through a two-stage process. For example, please refer to the document "Experimental method for polymer synthesis" (the method described in the first issue of the first issue of the Otsuka Ryokan, Ltd.), or the publication of the 2001-89533 Manufactured by the method described in the above.

Specifically, the steps regarding the first stage are first explained. A compound (Aa) and (Ab) of a copolymer (ie, a binder resin) obtained by copolymerizing the copolymers (Aa) and (Ab) are derivatized, a polymerization initiator, and a solvent are placed in a reaction vessel. The binder resin is obtained by substituting oxygen with nitrogen and stirring, heating, and holding in the absence of oxygen. Further, as the obtained resin, the solution after the reaction may be used as it is, or a solution which is concentrated or diluted may be used, or a solid (powder) may be used by a method such as re-sinking. The above-mentioned resin preferably has a weight average molecular weight in terms of polyethylene, preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin is within the above range, the coating property tends to be good, which is preferable.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the above resin is preferably from 1.1 to 6.0, more preferably from 1.2 to 4.0. When the molecular weight distribution is within the above range, the coating property tends to be excellent, which is preferable.

Next, explain the steps related to the second phase. Next, the atmosphere in the flask is replaced with air by nitrogen, and the component (Ac) having a molar number of 5 to 80 mol% based on the constituent component (Aa) is used as a carboxyl group and an epoxy group or an oxycyclobutane group. The reaction catalyst, for example, dimethylaminomethylphenol is 0.001 to 5% by mass based on the total amount of the monomers (Aa) to (Ac), and is used as a polymerization inhibiting agent, for example, hydroquinone. The total amount of the monomers (Aa) to (Ac) is 0.001 to 5% by mass based on the mass basis, and the resin and constituents can be obtained by reacting at 60 to 130 ° C for 1 to 10 hours. (Ac) reaction. However, similarly to the polymerization conditions, the introduction method or the reaction temperature can be appropriately adjusted in consideration of the heat generation amount generated by the production equipment or the polymerization.

In the binder resin (A2-3), the ratio of the constituent components derived from the respective components to the total number of moles of the constituent components constituting the binder resin (A2-3) is in the range of the following molar ratio. good.

Constituent units derived from (A-a): 5~95 mol%

Constituent units derived from (A-c): 5~95 mol%

Further, the ratio of the above-mentioned constituent components is more preferably in the following range.

Constituent units derived from (A-a): 10~90 mol%

The constituent units derived from (A-c): 10~90 mol%

When the composition ratio is within the above range, the stability, the solvent resistance, the heat resistance, and the mechanical strength tend to be good.

The binder resin (A2-3) can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). It is manufactured by reference to the documents described in the literature.

Specifically, a compound which derivatizes the units (Aa) and (Ac) constituting the copolymer is metered, a polymerization initiator and a solvent are placed in a reaction vessel, and oxygen is replaced by nitrogen in the absence of oxygen by stirring. Heating, heat preservation, and obtaining a polymer. Moreover, the obtained copolymer may be directly used as a solution after the reaction, or may be a solution which is concentrated or diluted, or may be used as a solid (powder) by a method such as re-sinking.

The polymerizable compound (B) contained in the curable resin composition of the present invention may, for example, be a monofunctional monomer, a bifunctional monomer or another trifunctional or higher polyfunctional monomer.

Specific examples of the monofunctional monomer include mercaptophenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-ethylhexylcarbitol. (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, 2-(2-ethoxy ethoxy) Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonyl phenol (meth) acrylate, propoxylated fluorenyl group Phenol (meth) acrylate or N-vinyl pyrrolidone.

Further, specific examples of the bifunctional monomer include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,6-hexanediol II ( Methyl) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, triethylene glycol di(methyl) Acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A bis(acryloxyethyl)ether, ethoxylated bisphenol A (methyl) Acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate or 3-methylpentanediol di(meth)acrylate .

Specific examples of the other trifunctional or higher polyfunctional monomer include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and gin(2-hydroxyethyl)isocyanurate. Ester tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate Reaction of ester, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri(meth) acrylate with anhydride, dipentaerythritol penta (meth) acrylate and anhydride , trimellititol hepta (meth) acrylate and anhydride caprolactone denatured trimethylolpropane tri(meth) acrylate, caprolactone denatured pentaerythritol tri (meth) acrylate, caprolactone denatured ginseng (2- Hydroxyethyl)isocyanurate tri(meth)acrylate, Ester-modified pentaerythritol tetra(meth)acrylate, caprolactone denatured dipentaerythritol penta (meth) acrylate, caprolactone denatured dipentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol tetra(methyl) Acrylate, caprolactone denatured tripentaerythritol penta (meth) acrylate, caprolactone denatured tripentaerythritol hexa(meth) acrylate, caprolactone denatured tripentaerythritol hepta (meth) acrylate, caprolactone denature a reaction of pentaerythritol octa (meth) acrylate, caprolactone denatured pentaerythritol tri(meth) acrylate with an acid anhydride, a reaction of caprolactone denatured dipentaerythritol penta (meth) acrylate with an acid anhydride, or caprolactone Denatured tripentaerythritol penta (meth) acrylate with an acid anhydride or the like.

Further, in the present specification, caprolactone denature means a ring-opening or ring-opening polymerization in which a caprolactone is introduced between a site derived from an alcohol of a (meth) acrylate compound and a (meth) acryloxy group. Things.

In particular, it is preferred to use a polyfunctional monomer having two or more functional groups. These polymerizable compounds (B) may be used singly or in combination of two or more.

The content of the polymerizable compound (B) is preferably from 1 to 70% by mass, and more preferably from 5 to 60% by mass, based on the total of the binder resin (A) and the polymerizable compound (B). . When the content of the polymerizable compound (B) is within the above range, the strength, smoothness, letterability, and mechanical strength of the coating film and the pattern tend to be good, which is preferable.

The polymerization initiator (C) contained in the curable resin composition of the present invention is a compound which starts polymerization by the action of light or heat, and is a bisimidazole compound, an acetophenone compound, a triazine compound, or a mercapto group. A phosphine oxide compound or an anthraquinone compound is preferred, and a bisimidazole compound is particularly excellent in sensitivity.

The above biimidazole compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole (for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2- Chlorophenyl) 4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxybenzene) Bis-imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)bisimidazole (for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204, etc.), 4, The imidazole compound in which the phenyl group at the 4', 5'-position is substituted with an alkoxycarbonyl group (for example, JP-A-7-10913, etc.), etc., preferably 2,2'-bis(2-chlorophenyl) )-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbisimidazole.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, and 2-hydroxy-1. -[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionium) -benzyl]-phenyl}-2-methyl-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholinyl-1-(4-methyl sulfonate Mercapto)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 2-(2-methylbenzyl) -2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-ethylbenzyl 2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4- Morpholinylphenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,3 -Dimethylbenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethyl Amino-1-(4-morpholinylphenyl)-butanone, 2-(2-chlorobenzyl)- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinylbenzene Butyl ketone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(4-chlorobenzyl)-2 -Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl) -butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methoxybenzyl)- 2-Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholine Phenylphenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl 4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2- Dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4- An oligomer of morpholinylphenyl)-butanone or 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

The aforementioned triazine-based compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis(trichloro). Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-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)ethynyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Ethynyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethynyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethynyl]-1,3,5-triazine Wait.

The above-mentioned mercaptophosphine oxide-based starter may, for example, be 2,4,6-trimethylbenzylidenediphenylphosphine oxide.

The above-mentioned oxime compound may, for example, be O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, a compound represented by the formula (IV), a compound represented by the formula (V), or the like.

A photopolymerization initiator or the like can be used in combination as long as the effect of the present invention is not impaired. Examples of the photopolymerization initiator include a benzoin compound, a benzophenone compound, and a thioxanthone compound.

More specifically, the following compounds may be mentioned, and these may be used individually or in combination of 2 or more types.

The aforementioned benzoin-based compound may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether.

Examples of the benzophenone-based compound include benzophenone, methyl o-benzyl benzoate, 4-phenylbenzophenone, and 4-benzylindolyl-4'-methyldiphenyl. a sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone.

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

Other examples thereof include 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, anthracene, methyl phenylglyoxylate or a titanocene compound. Photopolymerization initiator.

Further, as a photopolymerization initiator having a group capable of causing chain transfer, a photopolymerization initiator described in JP-A-2002-544205 can be used.

The photopolymerization initiator having a group which can cause a chain transfer, for example, is a photopolymerization initiator of the following formula (5) to the following formula (10).

Further, a light and/or thermal cationic polymerization initiator can be used.

The photo-and/or thermal cationic polymerization initiator may be composed of a phosphonium cation and an anion derived from a Lewis acid.

Specific examples of the phosphonium cation include diphenyl hydrazine, bis(p-benzyl) fluorene, bis(p-tert-butylphenyl) fluorene, and bis(p-octylphenyl) fluorene. , bis(p-octadecylphenyl)fluorene, bis(p-octyloxyphenyl)fluorene, bis(p-octadecyloxyphenyl)fluorene, phenyl (p-eighteen (oxyphenyl) hydrazine, (p-benzyl) (p-isopropylphenyl) fluorene, triphenyl sulfonium, ginseng (p-benzyl) hydrazine, ginseng (p-isopropylphenyl)鋶, ginseng (2,6-dimethylphenyl) fluorene, ginseng (p-tert-butylphenyl) fluorene, ginseng (p-cyanophenyl) fluorene, ginseng (p-chlorophenyl) hydrazine , dimethyl (methoxy) hydrazine, dimethyl (ethoxy) hydrazine, dimethyl (propoxy) hydrazine, dimethyl (butoxy) hydrazine, dimethyl (octyloxy) Anthracene, dimethyl (octadecyloxy) hydrazine, dimethyl (isopropoxy) hydrazine, dimethyl (tert-butoxy) hydrazine, dimethyl (cyclopentyloxy) fluorene, two Methyl (cyclohexyloxy) fluorene, dimethyl (fluoromethoxy) hydrazine, dimethyl (2-chloroethoxy) hydrazine, dimethyl (3-bromopropoxy) hydrazine, dimethyl (4-cyanobutoxy)anthracene, dimethyl(8-nitrooctyloxy)anthracene, dimethyl(18-trifluoromethyloctadecyloxy)anthracene, dimethyl (2- Isopropoxy-yl) sulfonium, or dimethyl (see (trichloromethyl) methyl) sulfonium and the like.

Preferred ruthenium cations are bis(p-benzyl)fluorene, (p-benzyl)(p-isopropylphenyl)fluorene, bis(p-tert-butylphenyl)fluorene, and three. Phenylhydrazine or ginseng (p-tert-butylphenyl) hydrazine.

Specific examples of the anion derived from the Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate or decyl (pentafluorophenyl) borate. Preferred examples of the anion derived from the Lewis acid include hexafluoroantimonate or quinone (pentafluorophenyl) borate.

The above cerium cation and an anion derived from a Lewis acid may be used arbitrarily in combination.

Specific examples of the cationic polymerization initiator include diphenylphosphonium hexafluorophosphate, bis(p-benzyl)phosphonium hexafluorophosphate, and bis(p-tert-butylphenyl)phosphonium hexafluorophosphate. Phosphate, bis(p-octylphenyl)phosphonium hexafluorophosphate, bis(p-octadecylphenyl)phosphonium hexafluorophosphate, bis(p-octyloxyphenyl)phosphonium Fluorophosphate, bis(p-octadecyloxyphenyl)phosphonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl)phosphonium hexafluorophosphate, (p-benzyl) P-isopropylphenyl)phosphonium hexafluorophosphate, methylnaphthylphosphonium hexafluorophosphate, ethylnaphthylphosphonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, ginseng (p- Benzyl)phosphonium hexafluorophosphate, ginseng (p-isopropylphenyl)phosphonium hexafluorophosphate, ginseng (2,6-dimethylphenyl)phosphonium hexafluorophosphate, ginseng (p-tert-butyl) Phenyl hexafluorophosphate, ginseng (p-cyanophenyl)phosphonium hexafluorophosphate, ginseng (p-chlorophenyl)phosphonium hexafluorophosphate, dimethylnaphthylphosphonium hexafluorophosphate, Diethylnaphthylphosphonium hexafluorophosphate, dimethyl(methoxy)phosphonium hexafluorophosphate, dimethyl(ethoxy)phosphonium hexafluorophosphate, dimethyl(propoxy)phosphonium hexafluorophosphate Phosphate , dimethyl(butoxy)phosphonium hexafluorophosphate, dimethyl(octyloxy)phosphonium hexafluorophosphate, dimethyl(octadecyloxy)phosphonium hexafluorophosphate, dimethyl ( Isopropoxy)phosphonium hexafluorophosphate, dimethyl(tert-butoxy)phosphonium hexafluorophosphate, dimethyl(cyclopentyloxy)phosphonium hexafluorophosphate, dimethyl (cyclohexyloxy) Hexafluorophosphate, dimethyl(fluoromethoxy)phosphonium hexafluorophosphate, dimethyl(2-chloroethoxy)phosphonium hexafluorophosphate, dimethyl (3-bromopropoxy)鋶 hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18- Trifluoromethyloctadecyloxy)phosphonium hexafluorophosphate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluorophosphate, dimethyl (xyl (trichloromethyl)methyl) fluorene Fluorophosphate; diphenylphosphonium hexafluoroarsenate, bis(p-benzyl)phosphonium hexafluoroarsenate, bis(p-tert-butylphenyl)phosphonium hexafluoroarsenate, double (p-octylphenyl)phosphonium hexafluoroarsenate, bis(p-octadecylphenyl)phosphonium hexafluoroarsenate, bis(p-octyloxyphenyl)phosphonium hexafluoroarsenate Acid salt, double (p-octadecyl) Phenyl phenyl) hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) ruthenium hexafluoroarsenate, (p-benzyl) (p-isopropylphenyl) hydrazine Hexafluoroarsenate, methylnaphthylphosphonium hexafluoroarsenate, ethylnaphthylphosphonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, ginseng (p-benzyl)phosphonium hexafluorophosphate Arsenate, ginseng (p-isopropylphenyl)phosphonium hexafluoroarsenate, ginseng (2,6-dimethylphenyl)phosphonium hexafluoroarsenate, ginseng (p-tert-butylphenyl)鋶 hexafluoroarsenate, ginseng (p-cyanophenyl) hexafluoroarsenate, ginseng (p-chlorophenyl) hexafluoroarsenate, dimethylnaphthyl fluorene hexafluoroarsenate , diethylnaphthylphosphonium hexafluoroarsenate, dimethyl(methoxy)phosphonium hexafluoroarsenate, dimethyl(ethoxy)phosphonium hexafluoroarsenate, dimethyl (propoxy) Hexafluoroarsenate, dimethyl(butoxy)phosphonium hexafluoroarsenate, dimethyl(octyloxy)phosphonium hexafluoroarsenate, dimethyl(octadecyloxy)phosphonium Hexafluoroarsenate, dimethyl(isopropoxy)phosphonium hexafluoroarsenate, dimethyl(tert-butoxy)phosphonium hexafluoroarsenate, dimethyl(cyclopentyloxy)fluorene Hexafluoroarsenate, dimethyl(cyclohexyloxy)phosphonium hexafluoroarsenate, Dimethyl(fluoromethoxy)phosphonium hexafluoroarsenate, dimethyl(2-chloroethoxy)phosphonium hexafluoroarsenate, dimethyl(3-bromopropoxy)phosphonium hexafluoroarsenate Salt, dimethyl(4-cyanobutoxy)phosphonium hexafluoroarsenate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroarsenate, dimethyl (18-trifluoromethyl) Octadecyloxy)phosphonium hexafluoroarsenate, dimethyl(2-hydroxyisopropoxy)phosphonium hexafluoroarsenate, dimethyl(xyl(trichloromethyl)methyl)phosphonium hexafluorophosphate Arsenate; diphenylphosphonium hexafluoroantimonate, bis(p-benzyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, double (p-octylphenyl)phosphonium hexafluoroantimonate, bis(p-octadecylphenyl)phosphonium hexafluoroantimonate, bis(p-octyloxyphenyl)phosphonium hexafluoroantimonate Acid salt, bis(p-octadecyloxyphenyl)phosphonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl)phosphonium hexafluoroantimonate, (p-benzyl) (p-isopropylphenyl)phosphonium hexafluoroantimonate, methylnaphthylphosphonium hexafluoroantimonate, ethylnaphthylphosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate , ginseng (p-benzyl) hexafluoroantimonate, ginseng (p-isopropylphenyl) hexafluoroantimonate Reference (2,6-dimethylphenyl)phosphonium hexafluoroantimonate, ginseng (p-tert-butylphenyl)phosphonium hexafluoroantimonate, ginseng (p-cyanophenyl)phosphonium hexafluoroantimonate Acid salt, ginseng (p-chlorophenyl) hexafluoroantimonate, dimethylnaphthyl hydrazine hexafluoroantimonate, diethyl naphthyl fluorene hexafluoroantimonate, dimethyl (methoxy) Hexafluoroantimonate, dimethyl(ethoxy)phosphonium hexafluoroantimonate, dimethyl(propoxy)phosphonium hexafluoroantimonate, dimethyl(butoxy)phosphonium hexafluoroantimonate Salt, dimethyl(octyloxy)phosphonium hexafluoroantimonate, dimethyl(octadecyloxy)phosphonium hexafluoroantimonate, dimethyl(isopropoxy)phosphonium hexafluoroantimonate , dimethyl (tert-butoxy) hexafluoroantimonate, dimethyl (cyclopentyloxy) hexafluoroantimonate, dimethyl (cyclohexyloxy) hexafluoroantimonate , dimethyl (fluoromethoxy) hexafluoroantimonate, dimethyl (2-chloroethoxy) hexafluoroantimonate, dimethyl (3-bromopropoxy) hexafluoroantimony Acid salt, dimethyl(4-cyanobutoxy)phosphonium hexafluoroantimonate, dimethyl(8-nitrooctyloxy)phosphonium hexafluoroantimonate, dimethyl (18-trifluoro) Methyl octadecyloxy) hexafluoroantimonate, dimethyl (2-hydroxyiso) Oxy) hexafluoroantimonate, dimethyl (paras(trichloromethyl)methyl) hexafluoroantimonate; diphenyl sulfonium (pentafluorophenyl) borate, double (p- Benzyl)phosphonium (pentafluorophenyl)borate, bis(p-tert-butylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octadecylphenyl)phosphonium (pentafluorophenyl)borate, bis(p-octyloxyphenyl)phosphonium (pentafluorophenyl) Borate, bis(p-octadecyloxyphenyl)phosphonium (pentafluorophenyl)borate, phenyl (p-octadecyloxyphenyl)phosphonium (pentafluorophenyl) Borate, (p-benzyl) (p-isopropylphenyl) ruthenium (pentafluorophenyl) borate, methylnaphthyl fluorene (pentafluorophenyl) borate, ethyl naphthyl錪鎓肆(pentafluorophenyl)borate, triphenylsulfonium (pentafluorophenyl)borate, ginseng (p-benzyl)phosphonium (pentafluorophenyl)borate, ginseng (p-isopropyl Phenyl) quinone (pentafluorophenyl) borate, ginseng (2,6-dimethylphenyl) ruthenium (pentafluorophenyl) borate, ginseng (p-tert-butylphenyl) hydrazine Bis(pentafluorophenyl)borate, ginseng (p-cyanophenyl)indole (pentafluorophenyl)borate, ginseng (p-chlorophenyl)indole (pentafluorophenyl)borate, dimethylnaphthyl fluorene (pentafluorophenyl) borate, diethylnaphthyl fluorene (pentafluorophenyl) borate, Dimethyl(methoxy)phosphonium (pentafluorophenyl)borate, dimethyl(ethoxy)phosphonium (pentafluorophenyl)borate, dimethyl(propoxy)phosphonium (five Fluorophenyl)borate, dimethyl(butoxy)phosphonium (pentafluorophenyl)borate, dimethyl(octyloxy)phosphonium (pentafluorophenyl)borate, dimethyl ( Octadecyloxy)phosphonium (pentafluorophenyl)borate, dimethyl(isopropoxy)phosphonium (pentafluorophenyl)borate, dimethyl(tert-butoxy)hydrazine Pentafluorophenyl)borate, dimethyl(cyclopentyloxy)phosphonium (pentafluorophenyl)borate, dimethyl(cyclohexyloxy)phosphonium (pentafluorophenyl)borate, two Methyl (fluoromethoxy) ruthenium (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) ruthenium (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) (鋶肆)(pentafluorophenyl)borate, dimethyl(4-cyanobutoxy)indole (pentafluorophenyl)borate, dimethyl(8-nitrooctyloxy)anthracene Bis(pentafluorophenyl)borate, dimethyl (18-trifluoro) Octadecyloxy)indole (pentafluorophenyl)borate, dimethyl(2-hydroxyisopropoxy)phosphonium (pentafluorophenyl)borate, dimethyl (parasyl (trichloromethane) Preference is given to bis(p-benzyl)phosphonium hexafluorophosphate or (p-benzyl) (p-isopropylphenyl).錪鎓 hexafluorophosphate, bis(p-tert-butylphenyl)phosphonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, ginseng (p-tert-butylphenyl)phosphonium hexafluorophosphate Salt, bis(p-benzyl)phosphonium hexafluoroarsenate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroarsenate, bis(p-tert-butylphenyl錪鎓 hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, ginseng (pt-butylphenyl)phosphonium hexafluoroarsenate, bis(p-benzyl)phosphonium hexafluoroantimonate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Salt, ginseng (p-tert-butylphenyl) hexafluoroantimonate, bis(p-benzyl)phosphonium (pentafluorophenyl)borate, (p-benzyl) (p-isopropyl) Phenyl) quinone (pentafluorophenyl) borate, bis(p-tert-butylphenyl) fluorene, triphenyl sulfonium (five More preferably, fluorophenyl) borate, ginseng (p-tert-butylphenyl) ruthenium (pentafluorophenyl) borate, etc., more preferably bis(p-benzyl)phosphonium hexafluoroantimonate, (p-benzyl)(p-isopropylphenyl)phosphonium hexafluoroantimonate, bis(p-tert-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate Salt, ginseng (p-tert-butylphenyl) hexafluoroantimonate, bis(p-benzyl)phosphonium (pentafluorophenyl)borate, (p-benzyl) (p-isopropyl) Phenyl)phosphonium (pentafluorophenyl)borate, bis(p-tert-butylphenyl)phosphonium (pentafluorophenyl)borate, triphenylsulfonium (pentafluorophenyl) Borate or ginseng (p-tert-butylphenyl) ruthenium (pentafluorophenyl) borate.

Further, the polymerization start aid (C-1) may be used in combination with the polymerization initiator (C), and the polymerization start aid may be used in combination, to the extent that the effects of the present invention are not impaired.

The polymerization initiation aid (C-1) may, for example, be an amine compound, a carboxylic acid compound, a polyfunctional thiol compound, a compound represented by the formula (III), or a formula (A-1) or a formula (A-2). Compounds, etc.

Examples of the amine compound include an aliphatic amine compound such as triethanolamine, methyldiethanolamine or triisopropanolamine, methyl 4-dimethylaminobenzoate, and ethyl 4-dimethylaminobenzoate. , 4-dimethylamino benzoic acid isoamyl ester, 4-dimethylamino benzoic acid 2-ethylhexyl ester, benzoic acid 2-dimethylaminoethyl ester, N, N-dimethyl pair Aromatic amines such as toluidine, 4,4'-bis(dimethylamino)benzophenone (general name; Michlerone) or 4,4'-bis(diethylamino)benzophenone Amine compound.

The above carboxylic acid compound may, for example, be phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, or Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio An aromatic heteroacetic acid such as acetic acid, N-naphthylglycine or naphthyloxyacetic acid.

The above polyfunctional thiol compound is a compound having two or more sulfonyl groups in the molecule. In particular, a compound having two or more sulfonyl groups bonded to a carbon atom of two or more aliphatic hydrocarbon groups is more preferable because the sensitivity of the curable resin composition of the present invention can be increased.

Specific examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylthiolbenzene, butanediol dithiopropionate, butanediol bis-mercaptoacetic acid. Ester, ethylene glycol bis-mercaptoacetate, trimethylolpropane decyl acetate, butanediol dithiopropionate, trimethylolpropane thiopropionate, trimethylolpropane Mercaptoacetate, pentaerythritol thiopropionate, pentaerythritol thioacetate, hydroxyethyl thiopropionate, pentaerythritol bismuth (3-mercaptobutyrate) or 1,4-bis (3- Mercaptobutyloxy)butane and the like.

The content of the polyfunctional thiol compound is preferably from 0.5 to 20% by mass, and more preferably from 1 to 15% by mass, based on the polymerization initiator (C). When the content of the polyfunctional thiol compound is in the above range, the sensitivity tends to be high, which is preferable.

A compound represented by the following formula (III) can also be used as the polymerization initiation aid (C-1).

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

Y represents an oxygen atom or a sulfur atom.

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

R ²² represents an alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom or an aromatic group which may be substituted by a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

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

The aromatic ring having 6 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring or a pentylbenzene ring. , hexylbenzene ring, cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene Ring, bromine naphthalene ring, and the like.

The alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl-n-propyl group. , tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl- N-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl and the like.

The alkyl group having 1 to 12 carbon atoms which may be substituted by a halogen atom may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl group. Base-n-propyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1 - dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n- Butyl, 2-chloro-n-butyl, 3-chloro-n-butyl and the like.

The aromatic group which may be substituted by a halogen atom may, for example, be phenyl, chlorophenyl, dichlorophenyl, bromophenyl, dibromophenyl, chlorobromophenyl, biphenyl, chlorobiphenyl or dichlorobiphenyl. Base, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl and the like.

Specific examples of the compound represented by the formula (III) include 2-benzylindolyl-3-methyl-benzothiazoline and 2-benzylidenemethylene-3-methyl-naphthalene. And [2,1-d]thiazoline, 2-benzylindolyl-3-methyl-naphtho[1,2-d]thiazoline, 2-benzylbenzylidene-3-methyl -naphtho[2,3-d]thiazoline, 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline, 2-(1-naphthylmethylidene methylene)- 3-methylbenzothiazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-5-phenylbenzothiazoline, 2-(1-naphthylmethylidene methylene) 3-methyl-5-phenylbenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-fluorobenzothiazoline, 2-(1-naphthoquinone) Benzylmethyl)-3-methyl-5-fluorobenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzothiazoline, 2-(1 -naphthylmethylidenemethyl)-3-methyl-5-chlorobenzothiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-bromobenzothiazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-bromobenzothiazoline, 2-(4-biphenyldimethylbenzylidene)-3-methylbenzothiazole Porphyrin, 2-(4-biphenyldimethylbenzylidene)-3-methyl-5-phenylbenzothiazoline, 2-(2-naphthoquinone) Benzylmethyl)-3-methyl-naphtho[2,1-d]thiazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-naphtho[1,2-d Thiazoline, 2-(4-biphenyldimethylbenzylidene)-3-methyl-naphtho[2,1-d]thiazoline, 2-(4-biphenyldimethylene) 3-methyl-naphtho[1,2-d]thiazoline, 2-(p-fluorobenzylidenemethylene)-3-methyl-naphtho[2,1-d]thiazoline , 2-(p-Fluorobenzylidene methylene)-3-methyl-naphtho[1,2-d]thiazoline, 2-benzylbenzylidene-3-methyl-naphtho[2] , 1-d]oxazoline, 2-benzylindolyl-3-methyl-naphtho[1,2-d]oxazoline, 2-benzylindenylmethylene-3-methyl- Naphtho[2,3-d]oxazoline, 2-(2-naphthylmethylidenemethyl)-3-methylbenzoxazoline, 2-(1-naphthylmethylidene) 3-methylbenzoxazoline, 2-(2-naphthylmethylidenemethyl)-3-methyl-5-phenylbenzoxazoline, 2-(1-naphthylmethyl) Methyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-fluorobenzoxazoline, 2-( 1-naphthylmethylidene methylene)-3-methyl-5-fluorobenzoxazoline, 2-(2-naphthylmethylidenemethylene)-3-methyl-5-chlorobenzoxan Oxazoline, 2-(1-naphthylmethylidene methylene)-3-methyl-5-chlorobenzoxime Oxazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-5-bromobenzoxazoline, 2-(1-naphthylmethylidenemethyl)-3-methyl- 5-bromobenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(4-biphenyldimethylphenyl) Methyl)-3-methyl-5-phenylbenzoxazoline, 2-(2-naphthylmethylidene methylene)-3-methyl-naphtho[2,1-d]oxazoline , 2-(2-naphthylmethylidene methylene)-3-methyl-naphtho[1,2-d]oxazoline, 2-(4-biphenyldimethylbenzylidene)-3 -methyl-naphtho[2,1-d]oxazoline, 2-(4-biphenyldimethylidene methylene)-3-methyl-naphtho[1,2-d]oxazoline , 2-(p-fluorobenzylidene methylene)-3-methyl-naphtho[2,1-d]oxazoline, 2-(p-fluorobenzylidenemethylene)-3-methyl Alkyl-naphtho[1,2-d]oxazoline and the like.

Wherein 2-(2-naphthylmethylidene methylene)-3-methylbenzothiazoline represented by formula (III-1), 2-benzylindenyl represented by formula (III-2) Methyl-3-methyl-naphtho[1,2-d]thiazoline and 2-(4-biphenyldimethylbenzylidene)-3-methyl- represented by formula (III-3) Naphtho[1,2-d]thiazoline and 2-benzylindolyl-3-methyl-benzothiazoline are preferred.

The polymerization initiation aid (C-1) may be a compound selected from at least one selected from the group consisting of the formula (A-1) and the formula (A-2).

In the formula (A-1) and the formula (A-2), the ring X ³¹ and the ring X ³² each independently represent an aromatic ring having 6 to 12 carbon atoms. Y ³¹ and Y ³² represent an oxygen atom or a sulfur atom.

R ³¹ and R ³² represent an alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The aromatic ring having 6 to 12 carbon atoms may, for example, be a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring or a ring. Hexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromine ring, A phenanthrene ring, a chrysene ring, a fluorenyl ring, a benzo[a]anthracene ring, a benzo[e]fluorene ring, an anthracene ring, and derivatives thereof.

The alkyl group having 1 to 12 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl-n-propyl group or a 2-methyl-n-propyl group. , tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n -propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, n-hexyl, cyclohexyl, 1-chloro-n-butyl, 2-chloro -n-butyl, 3-chloro-n-butyl and the like.

Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a hydroxyphenyl group, an alkoxyphenyl group, and a biphenyl group. , chlorobiphenyl, dichlorobiphenyl, bromophenyl, dibromophenyl, naphthyl, chloronaphthyl, dichloronaphthyl, bromonaphthyl, dibromonaphthyl, hydroxynaphthyl and the like.

Specific examples of the compound represented by the formula (A-1) or the formula (A-2) include dimethoxynaphthalene, diethoxynaphthalene, dipropoxynaphthalene, diisopropoxynaphthalene, and dibutoxy Di-alkoxy naphthalene dimethoxy hydrazine, diethoxy hydrazine, dipropoxy hydrazine, diisopropoxy fluorene, dibutoxy fluorene, dipentyl oxy fluorene, dihexyloxy Base, methoxyethoxy oxime, methoxypropoxy oxime, methoxyisopropoxy oxime, methoxybutoxy oxime, ethoxy propoxy oxime, ethoxy isopropyloxy a dialkoxy oxime dimethoxy thick four based on ruthenium, ethoxybutoxy oxime, propoxy oxime oxime, propoxy oxy oxime, isopropoxy butyl oxime or the like Benzene, diethoxy condensed tetraphenyl, dipropoxy fused tetraphenyl, diisopropoxy fused tetraphenyl, dibutoxy fused tetraphenyl, etc., but not limited This is the case.

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

Further, the content of the polymerization initiation aid (C-1) is preferably from 0.01 to 50% by mass, and more preferably from 0.1 to 40% by mass, based on the same criteria as described above.

The content of the compound represented by at least one of the groups of the formula (A-1) and the formula (A-2) is 50 to 100% based on the content of the polymerization initiation aid (C-1). Preferably, it is preferably 60 to 100%, more preferably 65 to 100%. When the content of the compound represented by at least one of the formulas (A-1) and (A-2) is within the above range, when a coating film is formed using the curable resin composition containing the coating film, the coating film is formed. The transparency is good, so it is preferable.

When the total amount of the polymerization initiator (C) is within the above range, the curable resin composition has high sensitivity, and the strength of the coating film or pattern formed using the above-mentioned curable resin composition, the above-mentioned coating film or pattern The smoothness in the surface tends to be good, so it is preferable. In addition, when the amount of the polymerization start aid (C-1) is within the above range, the sensitivity of the obtained curable resin composition is higher, and the productivity of the pattern formed using the above-described curable resin composition is obtained. It is better to promote the tendency.

The curable resin composition of the present invention contains a solvent (D). The solvent (D) is exemplified by 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, and ethylene glycol. Monopropyl ether and ethylene glycol monoalkyl ether like ethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; methyl cellosolve acetate, ethyl cellosolve acetate, ethylene Glycol alkyl ether acetates such as alcohol monobutyl ether acetate, ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Alkyl glycol alkyl ether acetates such as monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc.; propylene glycol monomethyl ether, propylene glycol monoethyl ether Propylene glycol monoalkyl ethers such as propylene glycol monopropyl ether and propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol Propylene glycol dialkyl ether propylene glycol methyl ether propionate such as methyl ether or propylene glycol ethyl propyl ether, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate a propylene glycol alkyl ether propionate; a butyl glycol monoalkyl ether of methoxybutyl alcohol, ethoxybutyl alcohol, propoxy butyl alcohol, butoxybutyl alcohol; Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxy butyl acetate, butoxybutyl acetate; methoxy Butanediol monoalkyl ether propionates such as butyl propionate, ethoxybutyl propionate, propoxy butyl propionate, butoxybutyl propionate; dipropylene glycol II a dipropylene glycol dialkyl ether such as methyl ether, dipropylene glycol diethyl ether or dipropylene glycol methyl ethyl ether; an aromatic hydrocarbon such as benzene, toluene, hydrazine or symmetrical trimethylbenzene; methyl ethyl ketone; a ketone such as acetone, methyl amyl ketone, methyl isobutyl ketone or cyclohexanone; an alcohol such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol or glycerin; Acetic acid , ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, glycolic acid Ester, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate Ethyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, Butyl propoxyacetate, methyl butoxyacetate, ethyl butoxide, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxyl Propyl propionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, 3-butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, An ester of methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate; tetrahydrofuran, piperane, etc. Cyclic ether groups; cyclic esters such as γ-butyrolactone.

Among the above-mentioned solvents, an ester solvent having a boiling point of 200 ° C or higher, preferably 200 to 300 ° C, an ether solvent, and an alcohol solvent are preferred from the viewpoints of coatability, printability, solubility, and drying property.

The ester solvent means an organic solvent having an ester bond and having no hydroxyl group.

Specific examples of the ester solvent include diethylene glycol monoethyl ether acetate (boiling point: 217 ° C), diethylene glycol monopropyl ether acetate (232 ° C), and diethylene glycol monobutyl Alkyl ether acetate (boiling point: 247 ° C), triacetin (boiling point: 260 ° C), preferably diethylene glycol monobutyl ether acetate (boiling point: 247 ° C), triacetin ( Boiling point 260 ° C).

The ether solvent refers to an organic solvent having an ether bond and having no ester bond and a hydroxyl group.

Specific examples of the ether solvent include diethylene glycol butyl methyl ether (boiling point: 212 ° C), tripropylene glycol dimethyl ether (boiling point: 215 ° C), and triethylene glycol dimethyl ether (boiling point: 216 ° C). , diethylene glycol dibutyl ether (boiling point 256 ° C), triethylene glycol butyl methyl ether (boiling point 261 ° C), tetraethylene glycol dimethyl ether (boiling point 275 ° C), preferably exemplified Alcohol dibutyl ether (boiling point 256 ° C), triethylene glycol butyl methyl ether (boiling point 261 ° C).

The alcohol solvent means an organic solvent having a hydroxyl group.

Specific examples of the above alcohol-based solvent include ethylene glycol monohexyl ether (boiling point: 208 ° C), ethylene glycol monoethyl 2-ethylhexyl ether (boiling point: 229 ° C), and ethylene glycol monophenyl ether (boiling point 245). °C), 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), diethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point 259 ° C), diethylene glycol mono 2-ethylhexyl ether (272 ° C), two 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), dipropylene glycol monopropyl ether (boiling point 212 ° C), dipropylene glycol monobutyl ether (boiling point 231 ° C), propylene glycol monophenyl ether (boiling point 243 ° C) Preferably, ethylene glycol monophenyl ether (boiling point 245 ° C), ethylene glycol monobenzyl ether (boiling point 256 ° C), diethylene glycol monopentyl ether, diethylene glycol monohexyl ether (boiling point) 259 ° C), propylene glycol monophenyl ether (boiling point 243 ° C).

These solvents (D) may be used alone or in combination of two or more kinds.

In the curable resin composition of the present invention, the amount of the solvent (D) is, for example, 20% by mass or more based on the mass fraction of the total amount of the binder resin (A), the polymerizable compound (B), and the solvent (D). It is less than 60% by mass, preferably 20% by mass or more and less than 50% by mass, more preferably 25% by mass or more and 50% by mass or less. When the content of the solvent (D) is less than 20% by mass, the viscosity of the curable composition is too high, and the transfer property in the printing method is deteriorated. On the other hand, when the viscosity is 80% by mass or more, the viscosity of the curable composition is too low, and the curable composition tends to remain on the intaglio plate, which makes it difficult to apply to the printing method.

The curable resin composition of the present invention does not substantially contain a coloring agent such as a pigment or a dye. In the curable resin composition of the present invention, the content of the coloring agent is, for example, less than 1% by mass, preferably less than 0.5% by mass, based on the total mass of the composition.

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

A compound classified as a pigment by Color Index (published by The Society of Dyers and Colourists), specifically, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31 Yellow pigments of 53, 53, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc. orange pigment; CI Pigment Red 9, 97, 105, 122, 123, Red pigments of 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc.; CI Pigment Blue 15, 15:3, 15:4 , 15:6, 60, etc. blue pigment; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. purple pigment; CI Pigment Green 7, 36, etc. green pigment; CI Pigment Brown 23, 25 Such as brown pigment; CI Pigment Black 1, 7 and other black pigments.

The curable resin composition of the present invention may be used in combination with a filler, other polymer compound, leveling agent, adhesion promoter, antioxidant, ultraviolet absorber, light stabilizer, anti-agglomerate, chain transfer agent, etc., as needed. additive.

Specific examples of the filler include glass, cerium oxide, and aluminum oxide.

Specific examples of the other polymer compound include curable resins such as epoxy resins and maleic imine resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and polyester. A thermoplastic resin such as a polyurethane or the like.

A commercially available surfactant can be used as the leveling agent, and examples thereof include a surfactant such as a polyfluorene-based, a fluorine-based, an ester-based, a cationic-based, an anionic-based, nonionic-based or amphoteric surfactant, and the like. It can be used in combination of 2 or more types. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, and grade 3 In addition to amine-denatured polyurethanes and polyvinylamines, there are also commercially available products such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), and Eftop (Mitsubishi Material Electronic Formation). (share)), Megafac (DIC), Fluorad (Sumitomo 3M (share) system), Asahiguide (Asahi (produced) system), Surflon (AGC SEIMI CHEMICAL), Solsperse (Zeneca) )), EFKA (made by CIBA), Ajisper PB821 (made by Ajinomoto).

The adhesion promoter is preferably a decane-based compound, and specific examples thereof include ethylene trimethoxy decane, ethylene triethoxy decane, ethylene ginseng (2-methoxyethoxy) decane, and N-(2-amino group B. 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane , 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc. .

Specific examples of the antioxidant include 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-( 2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4) -hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepine,3,9- Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanyloxy}-1,1-dimethylethyl]-2,4,8, 10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4'-butylene bis(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, octadecyl 3,3'-thiodi Propionate, pentaerythritol bismuth (3-lauryl thiopropionate), 1,3,5-gin (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5- Triazine-2,4,6(1H,3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"- (symmetric trimethyl-2,4,6-triyl)tri-p-cresol, penta Alcohols store [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'-B) Hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxyl -4-Butoxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-xin Benzyloxycarbonylethoxy]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-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl) -4-(1,1,3,3-tetramethylbutyl)phenol, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole or Alkoxybenzophenone and the like.

Specific examples of the photosensitizer include a polymer composed of succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethanol, N,N',N",N'. ''-肆(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4 , 7-dioxane-1,10-diamine, sebacic acid and bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidyl) ester 1,1-Dimethylethylhydroperoxide reactant, bis(1,2,2,6,6-pentylmethyl-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-piperidyl) sebacate.

The anti-agglomerate aggregate may, for example, be sodium polyacrylate.

Further, examples of the chain transfer agent include dodecyl mercaptan and 2,4-diphenyl-4-methyl-1-pentene.

The curable resin composition of the present invention has a low drying property and is less likely to cause dry foreign matter formed by solvent volatilization, and is excellent in storage stability even under high solid content, and is particularly suitable for a printing method.

As the printing method described above, it can be applied to a printing method known in the art, for example, an inkjet printing method, a rubber plate printing method, a gravure printing method, a lithography method, a screen printing method, or the like.

Further, the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and the average transmittance is 70% or more when the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. It is preferably 75% or more. Thereby, a transparent pattern or a coating film can be formed.

The curing conditions of the curable resin composition of the present invention can be appropriately selected depending on the type and content of each component of the composition, and are usually cured by light curing using an ultraviolet ray or the like, and heat curing using an oven or the like.

Further, the coating film having a thickness of 3 μm after heat curing (for example, 150 to 250 ° C for 0.1 to 3 hours) of the curable resin composition of the present invention is measured by using a spectrophotometer at a measurement wavelength of 400 to 700 nm. The transmittance is preferably 90% or more, preferably 95% or more. Thereby, a transparent pattern or a coating film can be formed.

The curable resin composition of the present invention can be carried out, for example, by coating, photocuring or heat curing on a substrate on which a glass substrate or a film substrate, a color filter or a drive circuit has been formed, by a printing method. Form a coating film or pattern.

Further, the curable resin composition is applied by a printing method on a substrate (usually glass) or a layer formed of a solid component of a curable resin composition which is formed in advance, and is composed of a coated curable resin. The material layer is subjected to prebaking to remove volatile components such as a solvent to obtain a smooth unhardened coating film (including a pattern). The thickness of the unhardened coating film at this time is about 1 to 6 μm. The uncured coating film thus obtained may also be irradiated with ultraviolet rays generated by a mercury lamp or a light-emitting diode.

Moreover, in the formation of the pattern, the line width can be appropriately controlled according to the gravure size.

Further, according to the need, it can be baked at 150 to 230 ° C for 10 to 180 minutes.

Using the curable resin composition of the present invention, a coating film or pattern can be formed on the substrate or on the color filter substrate through the above steps. This coating film or pattern can be used as a photolithographic spacer or a liquid crystal alignment protrusion, a partition wall, and a protective layer used in a liquid crystal display device.

By embedding the coating film or pattern thus obtained in a display device such as a liquid crystal display device, it is possible to manufacture a display device of excellent quality at a high yield.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited. In the examples, the content and the % and the parts expressed by the amount used are based on the mass basis unless otherwise specified.

[Synthesis Example 1]

In a flask of 1 L equipped with a reflow cooler, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto while stirring. Heat to 70 ° C. Next, 55 parts by mass of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the compound represented by the formula (II-1) 175 parts by mass of a molar ratio of 50:50 and 70 parts by mass of N-cyclohexylmaleimine were dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was used dropwise. The pump was dropped in a flask maintained at 70 ° C for 4 hours. On the other hand, 45 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and other solutions are used. The dropwise addition pump was dropped into the flask over 5 hours. After the completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 4 ° C and 70 ° C, and then cooled to room temperature to obtain a resin solution of a copolymer having a solid content of 32.6% by mass and an acid value of 34.3 mg-KOH/g. The obtained resin Aa had a weight average molecular weight Mw of 9,000 and a degree of dispersion of 2.01. 45 parts by mass of diethylene glycol n-butyl ether acetate was placed in 245 parts by mass of the resin solution, and 3-methoxybutyl acetate was concentrated and distilled off at 90 ° C under reduced pressure using a rotary evaporator. A solution of the resin Aa diethylene glycol n-butyl ether acetate having a solid content of 64.0% by mass was obtained. The acid value, the weight average molecular weight Mw, and the degree of dispersion are the same as those before concentration.

[Synthesis Example 2]

In a flask of 1 L equipped with a reflow cooler, a dropping funnel, and a stirrer, nitrogen was passed at 0.02 L/min to form a nitrogen atmosphere, and 305 parts by mass of 3-methoxybutyl acetate was added thereto while stirring. Heat to 70 ° C. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by the formula (I-1) and the formula (II-1)) The compound was mixed with 240 parts by mass of a molar ratio of 50:50 and dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a funnel for 4 hours, and then added dropwise thereto. In a flask at 70 ° C. On the other hand, 45 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in a solution of 225 parts by mass of 3-methoxybutyl acetate, and other solutions are used. The dropping funnel was dropped into the flask over 4 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 4 hours and 70 ° C, and then cooled to room temperature to obtain a resin solution of a copolymer having a solid content of 32.3 mass% and an acid value of 35.6 mg-KOH/g. The obtained resin Ab had a weight average molecular weight Mw of 9,100 and a degree of dispersion of 2.02. 45 parts by mass of diethylene glycol n-butyl ether acetate was added to 245 parts by mass of the resin solution, and 3-methoxybutyl acetate was concentrated and distilled off at 90 ° C under reduced pressure using a rotary evaporator. A diethylene glycol n-butyl ether acetate solution of a resin Ab of 64.0% by mass of solid was obtained. The acid value, the weight average molecular weight Mw, and the degree of dispersion are the same as those before concentration.

(Measurement of molecular weight)

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins Aa and Ab was carried out under the following conditions using a GPC method.

Device: K2479 (made by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0ml/min

Verifier; RI

The ratio of the weight average molecular weight and the number average molecular weight in terms of polyethylene obtained above was defined as the degree of dispersion (Mw/Mn).

[Example 1]

94 parts of a resin solution containing the resin Aa obtained in Synthesis Example 1 (60 parts in terms of solid content), 40 parts of dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.), 2-methyl-2-morpholine were mixed. One part of keto-1-(4-methylsulfonyl)propan-1-one and 34 parts of diethylene glycol n-butyl ether acetate were used to obtain a curable resin composition 1.

Next, the curable resin composition 1 is formed into the following pattern as follows. This method will be described with reference to FIG. 1.

First, the curable resin composition 1 (2) is dropped from the supply device (1) onto the intaglio plate (3) provided in the experimental printing machine (step a). The hardened resin composition 1 to be dropped is scraped off while the supply blade (4) is level, and the remaining curable resin composition 1 is scraped by the doctor blade (5) (step b). Next, the transfer cylinder (7) on which the transfer sheet (6) is attached to the outer peripheral surface is rotated on the intaglio plate (3), and the curable resin composition 1 is transferred onto the transfer sheet (6) surface (step c ). Next, the curable resin composition 1 on the surface of the transfer sheet (6) is transferred onto the surface of the substrate (8) (step d).

After transfer to the substrate (8), the film was dried at 100 ° C for 10 minutes, exposed to 100 mJ/cm ² (I line), and heated at 220 ° C / 20 minutes to obtain a pattern of 1.

[Embodiment 2]

In the first embodiment, the same operation as in the first embodiment was carried out except that the exposure step was omitted, and the pattern 2 was obtained from the curable resin composition 1.

[Example 3]

The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 2 and a pattern 3.

[Example 4]

The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 3 and a pattern 4.

[Example 5]

The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 4 and a pattern 5.

[Comparative Example 1]

The composition shown in Table 1 was carried out in the same manner as in Example 1 to obtain a curable resin composition 5. In the case where the curable resin composition 5 is used in the same manner as in the first embodiment, a large amount of the curable composition remains on the intaglio plate, and the pattern cannot be formed.

The following evaluations were performed on the curable resin compositions 1 to 5 and the patterns 1 to 6 obtained as described above. The results are shown in Table 1.

<Average transmittance of the composition>

For each of the curable resin compositions, an ultraviolet visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length; 1 cm) was used to measure the average transmittance in the range of 400 to 700 nm. (%).

<Average transmittance of film>

Each of the curable resin compositions was used to have a film thickness after curing of 3 μm, and a cured film was produced as follows.

The curable resin composition was diluted with diethylene glycol N-butyl ether acetate to have a solid content of 20% by mass. The film thickness after hardening was set to 3 μm by a spin coating method, and after prebaking at 100 ° C × 10 minutes, the film was heat-cured at 220 ° C × 20 minutes.

With respect to each of the obtained cured films, an average transmittance (%) in a range of 400 to 700 nm was measured using a microscopic spectrophotometer (OSP-SP200; manufactured by OLYMPUS).

A higher transmittance means less absorption.

<Shape shape>

The shape of each pattern was measured by a three-dimensional non-contact surface shape measuring system (manufactured by Micromap MM527N (manufacturing) system).

As a result of Examples 1 to 5 shown in Table 1, it was found that the curable resin composition of the present invention containing a predetermined amount of solvent can form a coating film and a pattern having a high transmittance by a printing method. On the other hand, in Comparative Example 1, the printing method could not be used.

Industrial availability

The curable resin composition of the present invention can form a coating film and a pattern having excellent transmittance by a printing method. Therefore, it can be suitably used for a coating film or pattern for use in a display device, such as a coating layer, a photolithographic spacer, an insulating film, a projection for liquid crystal alignment control, a coating film layer of a coloring pattern, and the like. form.

1‧‧‧Supply device

2‧‧‧Resin composition

3‧‧‧gravure

4‧‧‧supply blade

5‧‧‧scraping blade

6‧‧‧Transfer sheet

7‧‧‧Transfer胴

8‧‧‧Substrate

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

Claims (16)

A curable resin composition comprising a binder resin (A), a polymerizable compound (B), and a solvent (D), with respect to a binder resin (A), a polymerizable compound (B), and a solvent (D) The total amount of the solvent (D) is 20% by mass or more and 50% by mass or less. The curable resin composition according to the first aspect of the invention, wherein the amount of the solvent (D) is 25% by mass based on the total amount of the binder resin (A), the polymerizable compound (B) and the solvent (D). The above 50% by mass or less. The curable resin composition according to the first or second aspect of the invention, wherein the binder resin (A) is at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. (Aa), a copolymer obtained by polymerizing a monomer (Ac) having a cyclic ether structure having 2 to 4 carbon atoms. The curable resin composition according to claim 3, wherein the monomer (A-c) having a cyclic ether structure having 2 to 4 carbon atoms is a monomer having an epoxy group. The curable resin composition according to claim 4, wherein the single system having an epoxy group is a monomer having an aliphatic polycyclic epoxy group. The curable resin composition according to claim 5, wherein the single system having an aliphatic polycyclic epoxy group is selected from the group consisting of a compound represented by the formula (I) and a compound represented by the formula (II). a group of at least one compound, [In the formulae (I) and (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X ₁ and X; ₂ each independently represents an alkylene group having 1 to 6 carbon atoms which may have a single bond or a hetero atom. The curable resin composition according to claim 3, wherein at least one compound (Aa) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride is selected from the group consisting of aliphatic unsaturated carboxylic acids and A compound of at least one of a group of aliphatic unsaturated carboxylic anhydrides. The curable resin composition according to claim 6, wherein at least one compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) is selected from the formula ( a compound represented by I') and a compound of at least one of the compounds represented by the formula (II'), [In the formula (I') and the formula (II'), R ₁ ' and R ₂ ' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group] . The curable resin composition according to the first or second aspect of the patent application, wherein the solvent (D) has a boiling point of 200 ° C or higher and is contained. There is a solvent selected from at least one solvent selected from the group consisting of an ester solvent, an ether solvent, and an alcohol solvent. The curable resin composition according to claim 1 or 2, further comprising a polymerization initiator (C). The curative resin composition according to claim 10, wherein the polymerization initiator (C) contains a compound selected from the group consisting of a bisimidazole compound, an acetophenone compound, a triazine compound, and a mercaptophosphine oxide compound. A polymerization initiator for at least one compound in which the lanthanoid compounds are grouped. A use of the curable resin composition according to any one of claims 1 to 11, which is used for forming a coating film or a pattern. A coating film or a pattern which is formed by using the curable resin composition according to any one of the first to eleventh aspects of the invention. A display device comprising the coating film or pattern as described in claim 13 of the patent application. A method for producing a coating film or a pattern, which comprises applying the curable resin composition according to any one of the first to eleventh aspects of the invention to a substrate by a printing method, drying, and The step of heating to obtain a coating film or pattern. A method for producing a coating film or a pattern, which comprises applying the curable resin composition according to any one of the first to eleventh aspects of the invention to a substrate by a printing method, drying, and Exposure The step of obtaining a coating film or pattern according to the need for heating.