KR20110132518A - Curable resin composition - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to capable of reducing the cratering when coating an alignment agent solution on a pattern or a coating layer obtained from the composition. CONSTITUTION: A curable resin composition contains a resin, a titanium compound, and a solvent. The resin is an additional polymer containing the following: a structural unit originated from one compound selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride; and a structural unit originated from a monomer including C2-4 cyclic ether and a carbon-carbon unsaturated double bond.

Description

Curable Resin Composition {CURABLE RESIN COMPOSITION}

The present invention relates to a curable resin composition.

In recent liquid crystal display panels and the like, curable resin compositions are used to form photo spacers and overcoats. As such a curable resin composition, the curable resin composition containing the copolymer of an unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, and an aliphatic polycyclic epoxy compound, a polymeric compound, a polymerization initiator, and a solvent is known, for example. There is (patent document 1).

Japanese Laid-Open Patent Publication 2008-181087

However, the curable resin composition proposed conventionally is sufficient in the point that when the alignment film solution is apply | coated on the coating film or pattern obtained from the composition, the cratering of an alignment film solution generate | occur | produces, and it cannot apply | coat uniformly. It was not enough. The subject of this invention is providing the curable resin composition which provides the coating film and pattern which can reduce the cratering at the time of apply | coating an orientation film solution.

This invention provides the following [1]-[9].

[1] A resin (A) titanium compound (B) and a solvent (C) are contained,

 In the monomer which has a structural unit derived from at least 1 sort (s) chosen from the group which resin (A) consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a C2-C4 cyclic ether and a carbon-carbon unsaturated double bond. It is an addition polymer containing the structural unit which originates,

Curable property whose content of the structural unit derived from the C2-C4 cyclic ether and the monomer which has a carbon-carbon unsaturated double bond is 2 mol% or more and 95 mol% or less with respect to the structural unit whole quantity which comprises resin (A). Resin composition.

[2] The curable resin composition according to the above [1], wherein the titanium compound is a compound represented by formula (B-1).

[Formula 1]

[In formula (B-1), R <^3> , R <^4> , R <^5> and R <^6> represent a C1-C20 monovalent organic group independently of each other, and any two of R <^3> , R <^4> , R <^5> and R <^6> are May be bonded to each other to form a divalent organic group]

[3] Curable resin composition as described in said [1] or [2] whose content of a titanium compound (B) is 3 mass parts or more and 60 mass parts or less with respect to 100 mass parts of resin (A).

[4] Furthermore, curable resin composition in any one of said [1]-[3] containing at least 1 sort (s) chosen from the group which consists of a polymeric compound (D) and a polymerization initiator (E).

[5] The monomer having a cyclic ether having 2 to 4 carbon atoms and a carbon-carbon unsaturated double bond is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II) Curable resin composition in any one of said [1]-[4].

[Formula 2]

[In formula (I) and formula (II), R <^1> and R <^2> represents a hydrogen atom or a C1-C4 alkyl group mutually independently, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.

X ¹ and X ² independently represent a single bond, -R ^3- , * -R ³ -O-, * -R ³ -S-, * -R ³ -NH-.

R <^3> represents a C1-C6 alkanediyl group.

* Represents the number of bonds with O.]

[6] The curable resin composition according to any one of the above [1] to [5], wherein an average transmittance at a measurement wavelength of 400 to 700 nm is 70% or more.

[7] A coating film formed by using the curable resin composition according to any one of the above [1] to [6].

[8] A pattern formed using the curable resin composition according to any one of the above [1] to [6].

[9] A display device containing at least one selected from the group consisting of the coating film described in the above [7] and the pattern described in the above [8].

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

Curable resin composition of this invention contains resin (A), a titanium compound (B), and a solvent (C), and resin (A) is chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride. It is an addition polymer containing the structural unit derived from the at least 1 sort (s) which becomes, and the structural unit derived from the monomer which has a C2-C4 cyclic ether and a carbon-carbon unsaturated double bond, and the C2-C4 cyclic ether And content of the structural unit derived from the monomer which has a carbon-carbon unsaturated double bond is 2 mol% or more and 95 mol% or less with respect to the structural unit whole quantity which comprises resin (A).

In addition, in this specification, the compound illustrated as each component can be used individually or in combination unless there is particular notice.

Curable resin composition of this invention contains resin (A). Resin (A) is a structural unit derived from at least 1 sort (a) (Hereinafter, it may be called "(a)") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and C2-C. It is an addition polymer containing the structural unit derived from the monomer (b) (Hereinafter, it may be called "(b)") which has a cyclic ether of 4 and a carbon-carbon unsaturated double bond, and the C2-C4 ring. Content of the structural unit derived from the monomer which has a type ether and a carbon-carbon unsaturated double bond is 2 mol% or more and 95 mol% or less with respect to the structural unit whole quantity which comprises resin (A).

As resin (A) used for curable resin composition of this invention, for example,

Resin (A2-1): copolymer formed by superposing | polymerizing (a) and (b), and

Resin (A2-2): Monomer (c) copolymerizable with (a), (b) and (a) and (b) (but does not have a C2-C4 cyclic ether) (hereinafter "( c) "may be mentioned), and the copolymer etc. which superpose | polymerize, etc. are mentioned, As resin (A), resin (A2-1) is preferable.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2- N, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methyl ratio Bicyclo unsaturated compounds containing carboxyl groups such as cyclo [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hymic acid anhydride);

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

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in terms of copolymerization reactivity or alkali solubility.

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

(b) has, for example, a cyclic ether having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) It refers to a polymeric compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a carbon-carbon unsaturated double bond, and more preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group. .

As (b), for example, the monomer (b1) which has an oxiranyl group (Hereinafter, it may be called "(b1)"), and the monomer (b2) which has an oxetanyl group (hereinafter, it is called "(b2)"). The monomer (b3) (Hereinafter, it may be called "(b3)") which has a tetrahydrofuryl group, etc. are mentioned.

The monomer (b1) having an oxiranyl group refers to a polymerizable compound having an oxiranyl group. As (b1), the monomer (b1-1) (Hereinafter, it may be called "(b1-1)") and cyclic type which have a structure which epoxidized chain olefin, and a carbon-carbon unsaturated double bond, for example. The monomer (b1-2) (Hereinafter, it may be called "(b1-2)") which has a structure which epoxidized olefin, and a carbon-carbon unsaturated double bond is mentioned.

As (b1), it is preferable that it is a monomer which has an oxiranyl group and ethylenic carbon-carbon double bond, The monomer which has an oxiranyl group and a (meth) acryloyloxy group is more preferable, and has a (meth) acryloyloxy group (b1-2) is more preferable.

Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. -Vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (gly Cydyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl Styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene And the compound described in JP-A-7-248625.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, serotoside 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclo Hexylmethyl acrylate (for example, Cychrom A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cychroma M100; Daicel Chemical Industry Co., Ltd.) Production), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

(3)

[In Formula (I) and Formula (II), R <^1> and R <^2> represents a hydrogen atom or a C1-C4 alkyl group independently of each other, and even if the hydrogen atom contained in this alkyl group is substituted by the hydroxy group, do.

X ¹ and X ² independently represent a single bond, -R ^3- , * -R ³ -O-, * -R ³ -S-, * -R ³ -NH-.

R <^3> represents a C1-C6 alkanediyl group.

* Represents the number of bonds with O.]

Specifically as a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, etc. are mentioned.

As a hydroxyalkyl group, a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1- Methyl ethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

As R <^1> and R <^2> , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, and a 1,6-hexanedi A diary.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents the number of bonds with O), and a * -CH ₂ CH ₂ -O- group. and, more preferably, there may be mentioned a single bond, * -CH ₂ CH ₂ -O- group.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1)-Formula (I-15) are mentioned. Preferably formula (I-1), formula (I-3), 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) are mentioned.

[Formula 4]

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1)-Formula (II-15) are mentioned. Preferably formula (II-1), 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), and Formula (II-15) are mentioned.

 [Chemical Formula 5]

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively. Moreover, these can be mixed in arbitrary ratios. When mixing, the mixing ratio is a molar ratio, Preferably it is Formula (I): Formula (II), 5: 95-95: 5, More preferably, it is 10: 90-90: 10, Especially preferably, 20 : 80-80: 20.

The monomer (b2) which has an oxetanyl group represents the polymeric compound which has an oxetanyl group. As (b2), it is preferable that it is a monomer which has an oxetanyl group and a carbon-carbon unsaturated double bond, and the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, and 3-ethyl-3-methacryloyloxymethyl. Oxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl- 3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, etc. are mentioned.

The monomer (b3) which has a tetrahydrofuryl group represents the polymeric compound which has a tetrahydrofuryl group. As (b3), it is preferable that it is a monomer which has a tetrahydrofuryl group and a carbon-carbon unsaturated double bond, and the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable.

Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, etc. are mentioned, for example. Alkyl (meth) acrylates;

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

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

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

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

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto 2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonyl Cyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] Bicyclo unsaturated compounds, such as hepto-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

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

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

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

In resin (A2-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit which comprises resin (A2-1).

Structural unit derived from (a); 5-60 mol%, More preferably, it is 10-50 mol%

Structural unit derived from (b); 40-95 mol%, More preferably, 50-90 mol%

When the ratio of the structural unit of resin (A2-1) exists in said range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

As resin (A2-1), resin whose (b) is (b1) is preferable, Resin whose (b) is (b1-2) is more preferable, (b) The compound and formula which are represented by Formula (I) Resin which is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by (II) is more preferable.

Resin (A2-1) is a method as described in, for example, the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Co., Ltd., Chemical Co., Ltd., First Edition, First Printing, issued March 1, 1972). And the cited documents described in this document.

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

In addition, the obtained copolymer may use the solution after reaction as it is, the solution concentrated or diluted may be used, and what was taken out as solid (powder) by methods, such as reprecipitation, may be used. In particular, the solution after reaction can be used as it is by using the same solvent as the solvent (C) mentioned later as a solvent at the time of this superposition | polymerization, and a manufacturing process can be simplified.

In resin (A2-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total mole number of all the structural units which comprise resin (A2-2).

Structural unit derived from (a); 2-40 mol%, More preferably, it is 5-35 mol%

Structural unit derived from (b); 2-95 mol%, More preferably, it is 5-80 mol%

Structural unit derived from (c); 1-65 mol%, More preferably, it is 1-60 mol%

When the ratio of the structural unit of resin (A2-2) exists in the said range, storage stability, developability, solvent resistance, heat resistance, and mechanical strength tend to become favorable.

As resin (A2-2), the resin whose (b) is (b1) is preferable, The resin whose (b) is (b1-2) is more preferable, (b) The compound and formula which are represented by Formula (I) Resin which is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by (II) is more preferable.

Resin (A2-2) can be manufactured by the method similar to resin (A2-1).

The weight average molecular weight of polystyrene conversion of resin (A) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000. When the weight average molecular weight of resin (A) exists in the said range, applicability | paintability tends to become favorable, and film | membrane decrease does not generate | occur | produce well at the time of image development, and also tends to have good missing property of a non-pixel part at the time of image development. have.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (A) becomes like this. Preferably it is 1.1-6.0, More preferably, it is 1.2-4.0. When molecular weight distribution exists in the said range, it exists in the tendency which is excellent in developability.

The acid value of resin (A) becomes like this. Preferably it is 20-150, More preferably, it is 40-135, More preferably, it is 50-135. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (A), and can be obtained by titration using an aqueous potassium hydroxide solution.

Content of resin (A) becomes like this. Preferably it is 5-95 mass%, More preferably, it is 20-80 mass% with respect to the total amount of resin (A) and a polymeric compound (D), More preferably, it is 40-60 mass % to be. When content of resin (A) exists in said range, there exists a tendency for developability, adhesiveness, solvent resistance, and a mechanical characteristic to become favorable.

Curable resin composition of this invention contains a titanium compound (B). Examples of the titanium compound (B) include a compound represented by the formula (B-1), a complex containing a titanium atom, and the like.

  [Formula 6]

[In formula (B-1), R <^3> , R <^4> , R <^5> and R <^6> represent a C1-C20 monovalent organic group independently of each other, and any two of R <^3> , R <^4> , R <^5> and R <^6> are May be bonded to each other to form a divalent organic group]

As an organic group which shows R <^3> , R <^4> , R <^5> and R <^6> , an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an organic sulfonyl group, an organic phosphoryl group, and the group which combined these are mentioned, The sum total of carbon number is 1-20. The organic group may have an amino group. Especially, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 acyl group, a C6-C20 aryl group is preferable, a C1-C10 alkyl group, and a C3-C20 cycloalkyl group , C2-C20 acyl group is more preferable, and a C1-C10 alkyl group is more preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group and n-octyl group Etc. can be mentioned.

As a C3-C20 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclooctyl group, etc. are mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6 -Dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 4-phenylphenyl group, o- (dimethylphenylmethyl) phenyl group, m- (dimethylphenylmethyl) phenyl group, p- (dimethylphenylmethyl) phenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

Examples of the acyl group having 2 to 20 carbon atoms include an acetyl group, propionyl group, butyryl group, pivaloyl group, isobutyryl group, hexanoyl group, octanoyl group, dodecanoyl group, palmiroyl group, stearoyl group and isostearoyl group, Acryloyl group, methacryloyl group, etc. are mentioned.

Examples of the organic group having an amino group include an aminomethyl group, 2-aminoethyl group, N- (aminomethyl) aminomethyl group, N- (2-aminoethyl) -1-aminoethyl group, and N- (2-aminoethyl) -2- Amino ethyl group etc. are mentioned.

Examples of the organic sulfonyl group include a benzenesulfonyl group, o-toluenesulfonyl group, m-toluenesulfonyl group, p-toluenesulfonyl group, on-dodecylbenzenesulfonyl group, mn-dodecylbenzenesulfonyl group and pn-dodecylbenzenesulfon And a silyl group.

Organic phosphoryl groups include -P (O) (OC ₂ H ₅ ) ₂ , -P (O) (OC ₃ H ₇ ) ₂ , -P (O) (OC ₄ H ₉ ) ₂ , -P (O) (OC ₆ H ₁₃ ) ₂ , -P (O) (OC ₈ H ₁₇ ) ₂ , -P (O) -OP (O) (OC ₂ H ₅ ) ₂ , -P (O) (OC ₈ H ₁₇ ) -OP (O) (OH) (OC ₈ H ₁₇ ), and the like.

Moreover, as a divalent organic group formed by combining any two of R <^3> , R <^4> , R <^5>, and R <^6> , for example, a methylene group, an ethylene group, a propanediyl group, butanediyl group, a propenediyl group, etc. are mentioned. Can be mentioned.

As a compound represented by Formula (B), tetramethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tri-n-butoxy titanium monostearate, iso Propoxy citrate tristearate etc. are mentioned.

As a complex containing a titanium atom, diisopropoxybis (octylene glycolate) titanium, dioctyloxybis (octylene glycolate) titanium, diisopropoxy bis (acetylacetonato) titanium, propanedioxy titanium Bis (ethylaceto acetate) etc. are mentioned.

As a titanium compound (B), the compound represented by a formula (B-1) is preferable, and tetraisopropoxytitanium and tetrabutoxy titanium are more preferable.

It is preferable that content of a titanium compound (B) is 3 mass parts or more and 60 mass parts or less with respect to 100 mass parts of resin (A), It is more preferable that they are 7 mass parts or more and 60 mass parts or less, It is 15 mass parts or more and 60 mass parts or less It is more preferable, It is still more preferable that it is 25 mass parts or more and 60 mass parts or less, It is especially preferable that it is 40 mass parts or more and 60 mass parts or less, Most preferably, it is 45 mass parts or more and 55 mass parts or less, Most preferably, it is 5 mass parts or more and 50 If it is below a mass part, as shown in the Example, cratering can be reduced.

Curable resin composition of this invention contains a solvent (C).

Examples of the solvent that can be used in the present invention include ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (-COO- And -O- containing solvents), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate and ethyl butyrate Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As an ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl an Or a brush.

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

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

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

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

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

These solvents may be used independently or may be used in combination of 2 or more type.

The organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less is preferable among the said solvents from an applicability | paintability and a drying property. Especially, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-ethoxy propionate, 3-methoxy butyl acetate, and 3-methoxy- 1-butanol are preferable.

Content of the solvent (C) in curable resin composition becomes like this. Preferably it is 60-95 mass% with respect to curable resin composition, More preferably, it is 70-90 mass%. In other words, solid content of curable resin composition becomes like this. Preferably it is 5-40 mass%, More preferably, it is 10-30 mass%. Here, solid content means the quantity remove | excluding the solvent (C) from curable resin composition. When content of a solvent (C) exists in said range, there exists a tendency for the flatness of the film | membrane which applied curable resin composition to be high.

It is preferable that curable resin composition of this invention contains a polymeric compound (D).

The polymerizable compound (D) is a compound which can be polymerized by an active radical generated from the polymerization initiator (E), for example, a compound having a polymerizable carbon-carbon unsaturated bond, or the like, preferably a (meth) acrylic acid ester compound Can be mentioned.

As a polymeric compound (D) which has one polymerizable carbon-carbon unsaturated bond, the compound illustrated by said (a), (b) and (c) is mentioned, Especially, (meth) acrylic acid ester is desirable.

As a polymeric compound (D) which has two polymerizable carbon-carbon unsaturated bonds, 1, 3- butanediol di (meth) acrylate, 1, 3- butanediol (meth) acrylate, 1, 6- hexanediol di ( Meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth ) Acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, ethoxylated neo Pentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, and the like.

Examples of the polymerizable compound (D) having three or more polymerizable carbon-carbon unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyte. Anurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ( Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tri Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride Reactant of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritolhepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropanetri (meth) acrylate, caprolactone modified pentaeryte Lithitol tri (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol Penta (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (meth) acrylate, capro Lactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol Hepta (meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, caprolactone modified pentaerythritol tri (meth) acrylate and reactants of acid anhydride, caprolactone modified dipentaerythritol penta (meth) The reaction product of an acrylate and an acid anhydride, a caprolactone modified tripentaerythritol hepta (meth) acrylate, an acid anhydride, etc. are mentioned. Especially, a trifunctional or more than trifunctional monomer is preferable and dipentaerythritol hexa (meth) acrylate is more preferable.

Content of a polymeric compound (D) becomes like this. Preferably it is 5-95 mass%, More preferably, it is 20-80 mass% with respect to the total amount of resin (A) and a polymeric compound (D). When content of a polymeric compound (D) exists in the said range, there exists a tendency for the intensity | strength, smoothness, reliability, and mechanical strength of a sensitivity and a hardened pattern to become favorable.

It is preferable that curable resin composition of this invention contains a polymerization initiator (E). As a polymerization initiator (E), if it is a compound which starts superposition | polymerization by action of light or a heat | fever, it will not specifically limit, A well-known polymerization initiator can be used.

As a polymerization initiator (E), a biimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound is mentioned, for example. Moreover, you may use the optical and / or thermal cationic polymerization initiator (for example, what consists of onium cation and an anion derived from Lewis acid) of Unexamined-Japanese-Patent No. 2008-181087. Especially, it is preferable that it is at least 1 sort (s) chosen from the group which consists of a biimidazole compound, an acetophenone compound, and an oxime compound, and it is especially preferable that it is a biimidazole compound. If it is these polymerization initiators, there exists a tendency which becomes especially high sensitivity and is preferable.

As said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, eg, JP-A-6-75372, JP-A-6-75373, etc.), 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-open No. 62-174204, etc.), 4 The imidazole compound (For example, refer Unexamined-Japanese-Patent No. 7-10913 etc.) etc. in which the phenyl group of the 4'5, 5'-position is substituted by the carboalkoxy group. Preferably 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy) Hydroxyethoxy) phenyl] -2-methylpropane-1-one and 2-hydroxy-1- '4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl'-2 -Methyl-propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3 -Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl Butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholino Yl) butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino- 1- (4-morpholinophenyl) butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromobenzyl)- 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4- Chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholi Nophenyl) butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethyl And oligomers of amino-1- (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

As said triazine type compound, 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

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

Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-ethoxycarbonyloxy-1-phenylpropan-1-one-2 -Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- ｛2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanyl Methyloxy) benzoyl'-9H-carbazol-3-yl] ethane-1-imine, etc. are mentioned. You may use commercially available products, such as Irgacure OXE-01, OXE-02 (above, the Chiba Japan company), and N-1919 (the ADEKA company).

Moreover, as a polymerization initiator (E), Benzoin type compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoyl benzoate, 4- Such as phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone Benzophenone compounds; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, phenylglyoxylate, titanocene compound, etc. Can be mentioned. It is preferable to use these in combination with the polymerization start adjuvant (E1) mentioned later.

Moreover, you may use the polymerization initiator of Unexamined-Japanese-Patent No. 2002-544205 as a polymerization initiator which has group which can cause chain transfer.

As a polymerization initiator which has group which can cause said chain transfer, the compound of following formula (a)-(f) is mentioned, for example.

[Formula 7]

The polymerization initiator which has a group which can cause said chain transfer can be used also as a component (c) which comprises resin (A).

In the curable resin composition of this invention, a polymerization start adjuvant (E1) can be used with the polymerization initiator (E) mentioned above.

 As a polymerization start adjuvant (E1), it is preferable to use the compound represented, for example by Formula (III).

 [Formula 8]

In the formula (III), the dotted line represented by W ¹ represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.

Y ¹ represents -O- or -S-.

R <^4> represents a C1-C6 monovalent saturated hydrocarbon group.

R <^5> represents the C1-C12 saturated hydrocarbon group which may be substituted by the halogen atom, or the C6-C12 aryl group which may be substituted by the halogen atom.]

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned. Examples of the aromatic ring having 6 to 12 carbon atoms include a benzene ring and a naphthalene ring.

As a C6-C12 aromatic ring which may be substituted by the halogen atom, for example, a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring , Cyclohexylbenzene ring, chlorobenzene ring, dichlorobenzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene Ring etc. are mentioned.

As a C1-C6 saturated hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n, for example -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group And a cyclohexyl group may be mentioned.

As a C1-C12 saturated hydrocarbon group which may be substituted by the halogen atom, in addition to said C1-C6 saturated hydrocarbon group, for example, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 1-chlorobutyl group, 2-chlorobutyl group, 3-chlorobutyl group, etc. are mentioned.

Examples of the aryl group having 6 to 12 carbon atoms that may be substituted with a halogen atom include phenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, dibromophenyl group, chlorobromophenyl group, biphenyl group, chlorobiphenyl group, dichlorobiphenyl group and bromo. A phenyl group, a dibromophenyl group, a naphthyl group, a chloro naphthyl group, a dichloro naphthyl group, a bromonaphthyl group, a dibromonaphthyl group, etc. are mentioned.

Specifically as a compound represented by Formula (III),

2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] 3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [2,3-d] thiazoline, 2 -[2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylbenzothiazoline , 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene]- 3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2 -(1-naphthyl) ethylidene] -3-methyl-5-fluorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-chlorobenzo Thiazolin, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene ] -3-methyl-5-bromobenzothiazoline, 2- [2- Oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-bromobenzothiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzothia Sleepy, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methyl-5-phenylbenzothiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2,1-d] thiazoline, 2- [2-oxo-2- (4-phenylphenyl) ethyl Lidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] Thiazolin, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [1,2-d] thiazoline, 2- [2-oxo-2- (2- Phenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-methylnaphtho [1,2-d ] Oxazoline, 2- [2-oxo-2- (2-phenyl) ethylidene] -3-me Tilnaphtho [2,3-d] oxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (1 -Naphthyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2- Oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-phenylbenzooxazoline, 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5- Fluorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-fluorobenzooxazoline, 2- [2-oxo-2- (2-naph Tyl) ethylidene] -3-methyl-5-chlorobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl-5-chlorobenzooxazoline, 2- [ 2-oxo-2- (2-naphthyl) ethylidene] -3-methyl-5-bromobenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methyl -5-bromobenzooxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylbenzooxazoline, 2- [2-oxo-2- (4-phenylphenyl) Ethylidene] -3-methyl-5- Nylbenzooxazoline, 2- [2-oxo-2- (1-naphthyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (1 -Naphthyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [2, 1-d] oxazoline, 2- [2-oxo-2- (4-phenylphenyl) ethylidene] -3-methylnaphtho [1,2-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaphtho [2,1-d] oxazoline, 2- [2-oxo-2- (4-fluorophenyl) ethylidene] -3-methylnaph Saturday [1,2-d] oxazoline

Etc. can be mentioned.

Moreover, as a polymerization start adjuvant (E1), you may use the compound represented by Formula (IV) or Formula (V).

[Formula 9]

[Formula (IV) and formula (V) wherein ring W ^2, W ³ and W ⁴ represents the complex gorieul ring having 6 to 12 aromatic ring or 2 to 10 carbon atoms of which it may be optionally substituted with a halogen atom independently of one another. Y ² to Y ⁵ each independently represent -O- or -S-. R <^6> -R <^9> represents a C1-C12 monovalent saturated hydrocarbon group or a C6-C12 aryl group, and the hydrogen atom contained in this saturated hydrocarbon group and this aryl group is a halogen atom, a hydroxyl group, or C1-C6 May be substituted with an alkoxy group.

As an aromatic ring, the aromatic ring similar to what was illustrated by Formula (III) is mentioned, The hydrogen atom contained in the aromatic ring may be substituted by the halogen atom illustrated above.

As a hetero ring which may be substituted by the halogen atom, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a pyran ring, etc. are mentioned.

Examples of the monovalent hydroxy group-substituted saturated hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group and a hydroxybutyl group.

Examples of the hydroxy group-substituted aryl group include a hydroxyphenyl group and a hydroxy naphthyl group.

Examples of the monovalent alkoxy group substituted saturated hydrocarbon group include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, butoxymethyl group, ethoxyethyl group, ethoxypropyl group, propoxybutyl group and the like. .

As an alkoxy group substituted aryl group, a methoxyphenyl group, an ethoxy naphthyl group, etc. are mentioned.

As a compound represented by Formula (IV) and Formula (V), specifically,

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

9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, dipropoxycanthracene, diisopropoxycanthracene , Dibutoxy anthracene, dipentyloxy anthracene, dihexyloxy anthracene, methoxy ethoxy anthracene, methoxy propoxy thracene, methoxy isopropoxy canthracene, methoxy butoxy anthracene, ethoxy propoxy thracene, ethoxy isopro Dialkoxy anthracenes such as oxycanthracene, ethoxy butoxy anthracene, propoxy isopropoxy anthracene, propoxy butoxy anthracene and isopropoxy butoxy anthracene;

Dialkoxy naphthacenes such as dimethoxynaphthacene, diethoxy naphthacene, dipropoxynaphthacene, diisopropoxy naphthacene and dibutoxynaphthacene;

Etc. can be mentioned.

Moreover, a thioxanthone compound can also be used as a polymerization start adjuvant (E1). As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-, for example 4-propoxy thioxanthone etc. are mentioned.

Moreover, an amine compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (E1).

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, And aromatic heteroacetic acids such as chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxy acetic acid.

The content of the polymerization initiator (E) is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 10, based on the total amount of the resin (A) and the polymerizable compound (D). It is mass%. If content of a polymerization initiator (E) exists in said range, a pattern can be obtained with high sensitivity.

The usage-amount of a polymerization start adjuvant (E1) becomes like this. Preferably it is 0.1-10 mass% with respect to the total amount of resin (A) and a polymeric compound (D), More preferably, it is 0.3-7 mass%. When the quantity of a polymerization start adjuvant (E1) exists in said range, a pattern can be obtained with high sensitivity, and the pattern obtained has favorable shape.

Moreover, curable resin composition of this invention may contain the polyfunctional thiol compound (T) further. A polyfunctional thiol compound (T) means the compound which has a 2 or more sulfanyl group in a molecule | numerator. In particular, the use of a compound having two or more sulfanyl groups bonded to a carbon atom derived from an aliphatic hydrocarbon group tends to increase the sensitivity of the curable resin composition of the present invention.

Specific examples of the polyfunctional thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanylpropionate) and butanediolbis (3- Sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylprop Cypionate), trimethylol propane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris ( 3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1, 4-bis (3-sulfanyl butyloxy) butane, etc. are mentioned.

Content of a polyfunctional thiol compound (T) becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.5-7 mass% with respect to a polymerization initiator (E). When content of a polyfunctional thiol compound (T) exists in the said range, since the sensitivity of curable resin composition becomes high and developability tends to become favorable, it is preferable.

It is preferable that curable resin composition of this invention contains surfactant (F). As surfactant, a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned, for example.

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

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

As a fluorine type surfactant, surfactant which has a fluorocarbon chain | strand is mentioned. Specifically, Florinant (registered trademark) FC430, Copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper R30 (DIC) Co., Ltd.), F-top (registered trademark) EF301, copper EF303, copper EF351, copper EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Supron (registered trademark) S381, copper S382, copper SC101, copper SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemical Products Research Institute), etc. are mentioned.

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

Content of surfactant (F) is 0.001 mass% or more and 0.2 mass% or less with respect to curable resin composition, Preferably they are 0.002 mass% or more and 0.1 mass% or less, More preferably, they are 0.01 mass% or more and 0.05 mass% or less. By containing surfactant in said range, flatness of a coating film can be made favorable.

In the curable resin composition of this invention, you may use various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, a chain transfer agent, as needed.

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

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

When the curable resin composition of this invention is used as a coating film, the average transmittance of a coating film becomes like this. Preferably it is 90% or more, and it is more preferable to become 95% or more. This average transmittance | permeability was measured on the conditions of the measurement wavelength 400-700 nm using the spectrophotometer with respect to the coating film whose thickness after heat-hardening (for example, 100-250 degreeC, 5 minutes-3 hours) is 3 micrometers. Average value of the case. Thereby, the coating film excellent in transparency in visible region can be provided.

The curable resin composition of this invention is apply | coated on these board | substrates which formed board | substrates, such as glass, a metal, a plastic, color filters, various insulated or electrically conductive films, a drive circuit, etc., as mentioned later, for example, as mentioned later. It can be formed as. It is preferable that the coating film was dried and hardened. Moreover, the obtained coating film can also be patterned in a desired shape, and can also be used as a pattern. In addition, you may form and use these coating films or patterns as a part of component parts, such as a display apparatus.

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

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

Subsequently, it is preferable to dry or prebak and remove volatile components, such as a solvent. Thereby, a smooth uncured coating film can be obtained.

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material to be used, a use, etc., for example, about 1-6 micrometers is illustrated.

Further, light, for example, mercury lamp, ultraviolet light generated from a light emitting diode, or the like is irradiated through a mask for forming a desired pattern on the obtained uncured coating film. At this time, the shape of a mask is not specifically limited, Various shapes are mentioned. Moreover, the line width etc. can also be adjusted suitably according to mask size.

In a recent exposure machine, the bandpass filter which cuts out the light of less than 350 nm using the filter which cut | disconnects this wavelength range, or extracts the light of around 436 nm, 408 nm, and 365 nm vicinity is taken out these wavelength ranges. It can take out selectively using, and can irradiate a parallel light beam uniformly to the whole exposure surface. At this time, in order to perform accurate alignment of a mask and a base material, you may use apparatuses, such as a mask aligner and a stepper.

When manufacturing the coating film which does not have a pattern, you may expose to the whole surface, without using a mask, or you may not perform exposure.

Thereafter, the coating pattern is brought into contact with a developer to dissolve and develop a predetermined portion, for example, a non-exposed part, to obtain a target pattern shape. When manufacturing the coating film which does not have a pattern, it is preferable not to develop.

The developing method may be any of a puddle method, a dipping method, a spray method, and the like. In addition, you may tilt the base material at arbitrary angles at the time of image development.

As for the developing solution used for image development, the aqueous solution of a basic compound is preferable. The basic compound may be either an inorganic or organic basic compound.

Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, and carbonic acid. Potassium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, ammonia, etc. are mentioned.

As an organic basic compound, it is tetramethylammonium hydroxide, 2-hydroxyethyl trimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, for example. , Monoisopropylamine, diisopropylamine, ethanolamine and the like.

The concentration in the aqueous solution of these inorganic and organic basic compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the said basic compound may contain surfactant.

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

As nonionic surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester , Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.

Examples of the anionic surfactant include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, and dodecylbenzene sulfone. Alkyl aryl sulfonates, such as sodium acid and sodium dodecyl naphthalene sulfonate, etc. are mentioned.

As a cationic surfactant, amine salt, quaternary ammonium salt, etc., such as stearylamine hydrochloride and lauryl trimethylammonium chloride, etc. are mentioned, for example.

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

After image development, water washing may be performed and you may perform post-baking further as needed. The postbaking is preferably in a temperature range of 150 to 240 ° C. for 10 to 180 minutes.

Furthermore, it is preferable to irradiate an ultraviolet-ray after postbaking. As ultraviolet rays, deep ultraviolet rays are preferable. As an exposure amount, 10-10000 mJ / cm <2> is preferable. The coating film and / or pattern obtained from curable resin composition of this invention further laminate | stack and use another resin film. Usually, these resin films are laminated | stacked by apply | coating a resin solution on the said coating film and / or a pattern. By irradiating an ultraviolet-ray to the coating film and / or pattern after a postbaking, the cratering phenomenon of the resin solution apply | coated on a coating film and / or a pattern can be suppressed. The coating film manufactured by apply | coating curable resin composition of this invention, removing a volatile component, carrying out post-baking, and irradiating an ultraviolet-ray, does not generate | occur | produce cratering of the resin solution apply | coated on it well. Examples of the resin solution include an alignment film solution and the like.

The coating film or pattern obtained in this way is useful as a photo spacer used for a liquid crystal display device, and a patternable overcoat, for example. Moreover, at the time of patterning exposure with respect to an uncured coating film, a hole can be formed by using a photomask for hole formation, and it is useful as an interlayer insulation film. In addition, at the time of exposure to an uncured coating film, a transparent film can be formed by performing whole surface exposure, heat-hardening, or only heat-hardening, without using a photomask. This transparent film is useful as an overcoat. Moreover, it can also be used for display apparatuses, such as a touch panel. Thereby, it is possible to manufacture a display apparatus provided with a high quality coating film or a pattern with high yield.

Curable resin composition of this invention can reduce the cratering at the time of apply | coating an orientation film solution on the coating film and pattern obtained from the composition.

The curable resin composition of the present invention is a material for forming various films and patterns, for example, a transparent film, a pattern, a photo spacer, an overcoat, an insulating film, and a projection for controlling liquid crystal alignment, which form part of a color filter and / or an array substrate. , Micro lens, coat layer and the like are suitable. Moreover, the display apparatus provided with these color filters and / or array substrates, etc. which provide these coating films or patterns as a part of the component parts, etc., For example, a liquid crystal display device, an organic EL device Etc. can be used.

Example

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

Synthesis Example 1

In a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min in a nitrogen atmosphere, and 59 parts by mass of 3-methoxy-1-butanol and 81 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring.

Subsequently, 40 mass parts of methacrylic acid and 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by Formula (I-1) and compound represented by Formula (II-1) are molar ratio 50 :). 360 mass parts) was dissolved in 80 mass parts of 3-methoxy-1-butanol and 110 mass parts of 3-methoxybutyl acetate to prepare a solution. This solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 36 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 101 mass parts of 3-methoxy- 1-butanol, and 139 mass parts of 3-methoxybutyl acetates was melt | dissolved. Another dropping pump was used to drop into the flask over 5 hours. After completion of dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, whereby a solution of a copolymer (resin Aa) having a solid content of 42.5% by mass and an acid value of 56 mg-KOH / g was obtained. Got it. The weight average molecular weight (Mw) of obtained resin Aa was 7.6x10 <^3> , and molecular weight distribution (Mw / Mn) was 2.01.

[Formula 10]

Synthesis Example 2

In a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min in a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring. Subsequently, 60 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) in a molar ratio of 50: It was dissolved in 240 parts by mass and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetate, the flask over 4 hours using another dropping funnel. It was dripped inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, followed by copolymerization of a solid content of 32.6 mass% and an acid value of 110 mg-KOH / g (solid content conversion) (resin Ab). A solution of was obtained. The weight average molecular weight (Mw) of obtained resin Ab was 1.3x10 <^4> , and molecular weight distribution (Mw / Mn) was 2.50.

Synthesis Example 3

In a 1 L flask equipped with a reflux cooler, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min in a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added thereto. It heated to 70 degreeC, stirring. Subsequently, 55 parts by mass of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (compound represented by formula (I-1) and compound represented by formula (II-1) were molar ratios of 50: A mixture of 50.) 175 parts by mass and 70 parts by mass of N-cyclohexylmaleimide are dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution is used over 4 hours using a dropping pump. It dripped in the flask heated at 70 degreeC. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 mass parts of 3-methoxybutyl acetate, the flask over 5 hours using another dropping pump. It was dripped inside. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature. The solution of the copolymer (resin Ac) having a solid content of 32.6 mass% and an acid value of 34.3 mg-KOH / g of the solution was Got it. The weight average molecular weight (Mw) of obtained resin Ac was 13,600, and the number average molecular weight (Mn) was 5,400 and molecular weight distribution was 2.5.

Synthesis Example 4

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring.

Subsequently, 40 mass parts of methacrylic acid, the mixture of a 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by Formula (I-1) and a compound represented by Formula (II-1), molar ratio = 50:50) 340 parts by mass and 20 parts by mass of dicyclopentenyl acrylate (compound represented by the following formula (x1)) were dissolved in 190 parts by mass of diethylene glycol ethylmethyl ether to prepare a solution.

 The obtained solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethylmethyl ethers over 5 hours using another dropping pump. It was dripped into the flask.

After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature, thereby obtaining a solution of a copolymer (resin Ad) having a solid content of 41.8%. The weight average molecular weight (Mw) of obtained resin Ad was 9.6x10 <^3> , molecular weight distribution (Mw / Mn) was 2.02, and the acid value converted into solid content was 60 mg-KOH / g.

Synthesis Example 5

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 140 parts by mass of diethylene glycol ethylmethyl ether was added and heated to 70 ° C while stirring.

Subsequently, 40 mass parts of methacrylic acid, the mixture of a 3, 4- epoxy cyclocyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by Formula (I-1) and a compound represented by Formula (II-1), molar ratio = 50:50) 320 parts by mass and 40 parts by mass of dicyclopentanyl acrylate (compound represented by the following formula (x2)) were dissolved in 190 parts by mass of diethylene glycol ethylmethyl ether to prepare a solution.

 The obtained solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping pump.

On the other hand, the solution which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 240 mass parts of diethylene glycol ethylmethyl ethers over 5 hours using another dropping pump. It was dripped into the flask.

After dripping of the solution of a polymerization initiator was complete | finished, it hold | maintained at 70 degreeC for 4 hours, it cooled to room temperature after that, and obtained the solution of the copolymer (resin Ae) of 41.8% of solid content. The weight average molecular weight (Mw) of obtained resin Ae was 7.9x10 <^3> , molecular weight distribution (Mw / Mn) was 1.82, and the acid value converted into solid content was 60 mg-KOH / g.

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

Apparatus, K2479 (manufactured by Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

(Examples 1-7, 11-13)

<Adjustment of curable resin composition>

The components of Table 1 were mixed and the curable resin compositions 1-7 and 12-14 were obtained.

Each component in Table 1 is as follows.

Resin (A); Resin Aa obtained in Synthesis Example 1. The number of copies in Table 1 shows the mass part of solid content conversion.

Resin (A); Resin Ac. The number of copies in Table 1 shows the mass part of solid content conversion.

Resin (A); Resin Ad obtained in Synthesis Example 4. The number of copies in Table 1 shows the mass part of solid content conversion.

Resin (A); Resin Ae obtained in Synthesis Example 5. The number of copies in Table 1 shows the mass part of solid content conversion.

Compound (B); Ba; tetraisopropoxytitane (A-1; Nippon Soda Co., Ltd. product)

Compound (B); Bb; Tetrabutoxytitanium

Solvent (C); Ca; diethylene glycol butyl ether acetate

Solvent (C); Cb; 3-methoxybutyl acetate

Solvent (C); Cc; 3-methoxy-1-butanol

Solvent (C); Cd; diethylene glycol methyl ethyl ether

Polymeric compound (D); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

Additive 1; Fluorine type surfactant; Megapak F489 (made by DIC Corporation)

Additive 2; antioxidant; IRGANOX 3114 (made by Chiba Japan)

The solvent (C) is mixed so that the solid content of the curable resin composition becomes the "solid content (%)" in Table 1, and the values of the solvent components (Ca) to (Cc) in the solvent (C) are the solvent (C). The mass ratio in it is shown.

<Average transmittance of the composition>

The average in 400-700 nm using the ultraviolet-visible near-infrared spectrophotometer (V-650; Nippon Spectroscopy Co., Ltd. product) (quartz cell, optical path length; 1 cm) about the obtained curable resin compositions 1-7, respectively. The transmittance | permeability (%) was measured. The results are shown in Table 1.

<Mean transmittance of the film>

Using the obtained curable resin compositions 1-7, the film | membrane was produced on condition of the following so that the film thickness after hardening might be set to 3 micrometers, respectively.

The glass substrate (# 1737; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after postbaking might be set to 3.0 micrometers, and then prebaked for 3 minutes at 90 degreeC in a clean oven. Then, it heated at 230 degreeC for 20 minutes, and obtained the film | membrane.

About the obtained film | membrane, the average transmittance | permeability (%) in 400-700 nm was measured using the microscopic spectrophotometer (OSP-SP200; the product made by OLYMPUS). Higher transmittance means less absorption. The results are shown in Table 1.

<Formation of Coating Film>

Each obtained curable resin composition 1-7 was spin-coated on the glass substrate so that the film thickness after postbaking might be set to 2.0 micrometers using a spin coater, respectively. Thereafter, the resultant was dried under reduced pressure with a reduced pressure dryer (manufactured by Microtech Co., Ltd.) until the pressure was 66 Pa, and then prebaked at 80 ° C. for 2 minutes with a hot plate to dry. Furthermore, it heated for 20 minutes at 230 degreeC, and formed the coating film.

<Contact angle>

About the obtained coating film, the contact angle of ion-exchange water was measured using the contact angle meter (DGD Fast / 60; GBX Corporation make). Furthermore, the contact angle was measured similarly to the above after irradiating the light of exposure amount 1000mJ / cm <2> (254 nm standard) in air | atmosphere using the UV washing machine (made by Microtech Co., Ltd.) to the obtained coating film. The results are shown in Table 2.

The lower the contact angle is, the less likely cratering and nonuniformity are to occur when the coating film is formed separately on the coating film formed by the composition.

<Cratering>

Polyimide varnish (San Eva 5291; Nissan Chemical Industries, Ltd.) after irradiating the obtained coating film with the light of exposure amount 1000mJ / cm <2> (254 nm standard) in air | atmosphere using a UV washing machine (made by Microtech Co., Ltd.). (Preparation) was spin-coated so that the film thickness after application | coating may be 0.15 micrometer using a spin coater. The apply | coated polyimide varnish was visually observed, and it was determined by x that there was a cratering, and that there was no cratering. The results are shown in Table 2.

(Examples 8 to 10, Comparative Example 1)

<Adjustment of curable resin composition>

The components of Table 3 were mixed and the curable resin compositions 8-11 were obtained.

Each component in Table 3 is as follows.

Resin (A); Resin Ab obtained in Synthesis Example 2. The number of copies in Table 3 shows the mass part of solid content conversion.

Compound (B); Ba; tetraisopropoxytitane (manufactured by A-1 Nippon Soda Co., Ltd.)

Compound (B); Bb; Tetrabutoxytitanium

Polymerizable Compound (D); dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Gunpowder Co., Ltd.)

Polymerization initiator (E); Ea; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; Hodogaya Chemical Manufacture)

Polymerization initiation aid (E1); 2- [2-oxo-2- (2-naphthyl) ethylidene] -3-methylbenzothiazoline (compound represented by formula (III-1))

[Formula 11]

Polyfunctional Thiol (T); pentaerythritol tetrakis (3-sulfanylpropionate) (PEMP manufactured by Sakai Chemical Industry Co., Ltd.)

Solvent (C); Ca; propylene glycol monomethyl ether acetate

Solvent (C); Cb; ethyl 3-ethoxypropionate

Solvent (C); Cc; 3-methoxy-1-butanol

Solvent (C); Cd; 3-methoxybutyl acetate

Additive 1; polyether modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.)

Additive 2; IRGANOX 3114 (made by Chiba Japan Corporation)

The solvent (C) is mixed so that the solid content of the curable resin composition becomes the "solid content [%] of Table 1, and the values of the solvent components (Ca) to (Cd) in the solvent (C) are in the solvent (C). The mass ratio is shown.

<Contact angle>

About curable resin compositions 8-11, it carried out similarly to Example 1, and measured the contact angle. The results are shown in Table 4.

<Cratering>

About curable resin compositions 8-11, it carried out similarly to Example 1, and measured the contact angle. The results are shown in Table 4.

<Pattern formation>

The glass substrate (# 1737; manufactured by Corning Corporation) having a length and width of 2 inches was washed sequentially with a neutral detergent, water, and alcohol, and then dried. On this glass substrate, the curable resin composition was spin-coated so that the film thickness after postbaking might be set to 3 micrometers.

Then, the pressure reduction degree was dried under reduced pressure to 0.5 torr by the pressure reduction dryer (made by VCD Microtech Co., Ltd.). On a hot plate, it dried by prebaking at 80 degreeC for 2 minutes. After cooling, the gap between the substrate coated with the curable resin composition and the quartz glass photomask was 10 μm, and the exposure dose was measured under an atmospheric atmosphere using an exposure machine (TME-150RSK; Topcon Co., Ltd. light source; ultrahigh pressure mercury lamp). 100 mJ / cm 2 (405 nm standard) of light was irradiated. In addition, irradiation with the curable resin composition at this time was performed through the optical filter (LU0400; Asahi Spectrum Co., Ltd. make). As a photomask, a photomask in which a pattern (a square light-transmitting portion having one side of 19 μm was formed and the interval between the squares was 100 μm) (that is, a light-transmitting portion) was formed on the same plane was used.

After light irradiation, the coating film was immersed and stirred for 25 seconds at 25 ° C. for 100 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. Was carried out to obtain a pattern.

<Measurement of pattern width>

The width of the obtained pattern was measured by a three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100; manufactured by Ryoka System Co., Ltd.). About the pattern height, the pattern width of 5% height was measured from the board | substrate surface. The results are shown in Table 4.

<Mechanical Characteristics (Total Displacement and Recovery Rate)>

About the obtained pattern, the total displacement amount (micrometer) and the elastic displacement amount (micrometer) were measured using the dynamic ultramicro hardness tester (DUH-W201; Shimadzu Corporation make), and the recovery rate (%) was computed. It is possible to manufacture the liquid crystal panel excellent in intensity, so that a recovery rate is high. The results are shown in Table 4.

-Measuring conditions-

Test mode; load-unload test

Test force; 50 mN

Load speed; 4.41 mN / sec

Holding time; 5 sec

Indenter; cone indenter (diameter 50 μm)

Recovery rate (%); (elastic displacement amount (µm) / total displacement amount (µm)) × 100

When curable resin composition of this invention apply | coated the orientation film solution on the coating film and pattern obtained from the composition, it was confirmed that cratering is reduced.

By forming a coating film or a pattern using such a curable resin composition, and using them to manufacture a display apparatus, it becomes possible to improve a yield.

When curable resin composition of this invention apply | coats an oriented film solution on the coating film or pattern obtained from curable resin composition, cratering does not generate | occur | produce well.

Curable resin composition of this invention is a material for forming various films and patterns, for example, a transparent film, a pattern, a photo spacer, an overcoat, an insulating film, liquid crystal orientation control which comprise a part of a color filter and / or an array substrate. It is suitable for forming projections, microlenses, coat layers and the like. Moreover, the display apparatus provided with these color filters and / or array substrates, etc. which provide these coating films or patterns as a part of the component parts, etc., For example, a liquid crystal display device, an organic EL device Etc. can be used.

Claims (9)

Resin (A), a titanium compound (B), and a solvent (C) are contained,
In the monomer which has a structural unit derived from at least 1 sort (s) chosen from the group which resin (A) consists of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a C2-C4 cyclic ether and a carbon-carbon unsaturated double bond. It is an addition polymer containing the structural unit which originates,
Curable property whose content of the structural unit derived from the C2-C4 cyclic ether and the monomer which has a carbon-carbon unsaturated double bond is 2 mol% or more and 95 mol% or less with respect to the structural unit whole quantity which comprises resin (A). Resin composition. The method of claim 1,
Curable resin composition whose titanium compound is a compound represented by Formula (B-1).

[In formula (B-1), R <^3> , R <^4> , R <^5> and R <^6> represent a C1-C20 monovalent organic group independently of each other, and any two of R <^3> , R <^4> , R <^5> and R <^6> are May be bonded to each other to form a divalent organic group] The method of claim 1,
Curable resin composition whose content of a titanium compound (B) is 3 mass parts or more and 60 mass parts or less with respect to 100 mass parts of resin (A). The method of claim 1,
Furthermore, curable resin composition containing at least 1 sort (s) chosen from the group which consists of a polymeric compound (D) and a polymerization initiator (E). The method of claim 1,
Curable resin composition whose monomer which has a C2-C4 cyclic ether and a carbon-carbon unsaturated double bond is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by Formula (I) and a compound represented by Formula (II). .

[In formula (I) and formula (II), R <^1> and R <^2> represents a hydrogen atom or a C1-C4 alkyl group mutually independently, and the hydrogen atom contained in this alkyl group may be substituted by the hydroxy group.
X ¹ and X ² independently represent a single bond, -R ^3- , * -R ³ -O-, * -R ³ -S-, * -R ³ -NH-.
R <^3> represents a C1-C6 alkanediyl group.
* Represents the number of bonds with O.] The method of claim 1,
Curable resin composition whose average transmittance in measurement wavelength 400-700 nm is 70% or more. The coating film formed using the curable resin composition of Claim 1. The pattern formed using the curable resin composition of Claim 1. The display device containing at least 1 sort (s) chosen from the group which consists of a coating film of Claim 7 and the pattern of Claim 8.