KR101738161B1 - Photosensitive resin composition - Google Patents

Abstract

1. A photosensitive resin composition comprising a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D) and a surfactant (E)

The solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 175 캜 or lower,

The content of the surfactant (E) is 0.0025 to 0.0250% by weight based on 100% by weight of the photosensitive resin composition excluding the surfactant,

And a solid content of 10 to 30% by weight.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

In recent liquid crystal display panels and the like, the size of the substrate is becoming larger, and in order to form a transparent film or pattern such as a coat layer on the surface of the substrate, the photosensitive resin composition is formed by spin coating, slit & .

On the other hand, from the viewpoints of productivity improvement, response to a large screen, and the like, a method of forming a uniform coating film of high quality while saving the photosensitive resin composition solution has been researched.

In this background, selection of a solvent type is sought to form a coating film of excellent quality. For example, when a low boiling point solvent is used, the coating film is rapidly dried, but on the other hand, the evaporation of the solvent may cause a sudden boiling of minute bubbles contained in the composition for forming a coating film. Such dolbis emits bubbles on the surface of the coating film, resulting in defects in a crater shape.

Therefore, conventionally, a high boiling point solvent has been used as a solvent. For example, a photosensitive resin composition containing a high boiling point solvent such as diethylene glycol ethyl methyl ether (boiling point: 176 ° C) and benzyl alcohol (boiling point: 205 ° C) has been proposed (for example, Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2007-25645, paragraph 46, Table 1

However, even when a photosensitive resin composition using the above-mentioned high boiling point solvent is applied to a slit die coating method, which is a representative coating method, a high-quality coating film which does not necessarily cause cloudiness or defects can not be obtained.

It is an object of the present invention to provide a photosensitive resin composition capable of suppressing occurrence of defects or cloudiness caused by the dolby rubbing of a solvent and forming a uniform and high quality coating film over the entire coating film.

That is, the present invention provides the following [1] to [8].

[One]. 1. A photosensitive resin composition comprising a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D) and a surfactant (E)

The solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 175 캜 or lower,

The content of the surfactant (E) is 0.0025 to 0.0250% by weight based on 100% by weight of the photosensitive resin composition excluding the surfactant,

And a solid content of 10 to 30% by weight.

[2]. The photosensitive resin composition according to [1], wherein the solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of from 140 캜 to 175 캜.

[3]. The photosensitive resin composition according to [1] or [2], wherein the solvent (D) is a solvent containing an alcohol having 1 to 6 carbon atoms.

[4]. The photosensitive resin composition according to any one of [1] to [3], wherein the solvent (D) is a solvent containing 3-methoxybutanol.

[5]. The photosensitive resin composition according to any one of [1] to [4], wherein the surfactant (E) is at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant and a silicon surfactant having a fluorine atom.

[6]. A coating film formed using the photosensitive resin composition according to any one of [1] to [5].

[7]. A pattern formed by using the photosensitive resin composition according to any one of [1] to [5].

[8]. A display device comprising a coating film described in [6] and / or a pattern described in [7].

INDUSTRIAL APPLICABILITY The present invention can provide a photosensitive resin composition capable of suppressing the occurrence of defects or cloudiness caused by the dolvite in a solvent and forming a uniform and high quality coating film over the whole coating film.

The photosensitive resin composition of the present invention mainly comprises a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D) and a surfactant (E).

The resin (A) used in the photosensitive resin composition of the present invention is not particularly limited, and it is preferable that the resin (A1) is alkali soluble and the resin (A2) exhibiting reactivity by action of at least one of light and heat is desirable.

As the resin (A1), at least one kind (Aa) (hereinafter may be referred to as "(Aa)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a monomer (Ab) (note that (Aa) is excluded) (hereinafter may be referred to as "Ab"), and the like.

(A-a) include, for example, an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride, and specifically,

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

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these unsaturated dicarboxylic acids;

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- Esters;

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

- (hydroxymethyl) acrylic acid, and the like, and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Among them, acrylic acid, methacrylic acid or maleic anhydride are preferable in terms of copolymerization reactivity and alkali solubility.

These may be used alone or in combination of two or more. In the present specification, unless otherwise stated, the exemplified compounds, components, and agents may be used alone or in combination of two or more.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. Quot ;, " (meth) acryloyl ", and " (meth) acrylate "

(A-b)

Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

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

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (referred to in the art as dicyclopentanyl acrylate), dicyclopenta Acrylic acid cyclic alkyl esters such as oxyethyl acrylate and isobornyl acrylate;

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

Aryl acrylates such as phenyl acrylate and benzyl acrylate;

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

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

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] , 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto- 2,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 2,1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] 2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2 1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2 2,1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] , 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxine (5-tert-butoxycarbonylbicyclo [2.2.1] hept- 2,6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] Cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, and the like;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

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

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

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

(A1) obtained by copolymerizing (Aa) and (Ab) in the resin (A1) is such that the ratio of the constituent components derived from each other is in the molar fraction when the total number of moles of the constituent components constituting the resin (A1) Range. ≪ / RTI >

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

(A-b); 60 to 98 mol%

It is more preferable that the ratio of the constituent components is within the following range.

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

(A-b); 65 to 95 mol%

When the composition ratio is in this range, storage stability, developability and solvent resistance tend to be improved.

Resin (A1) can be synthesized by methods described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) (The same also in the resin (A2)).

Specifically, a predetermined amount of the units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent are put into a reaction vessel, oxygen is replaced by nitrogen, and the mixture is stirred, heated and kept warm in the absence of oxygen A polymer is obtained.

As the polymerization initiator used herein, any of those conventionally used in the art can be used. For example, a polymerization initiator (C) described later or the like can be used.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used. Alternatively, the copolymer may be taken out as a solid (powder) by re-precipitation or the like.

In particular, by using the solvent (D) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified (the same also in the resin (A2)).

The weight average molecular weight of the resin (A1) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the resin (A1) is within this range, the coating property tends to be good, the film is not easily reduced at the time of development, and the non-pixel portion tends to be satisfactory in the development.

The dispersion degree (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A1) are preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the degree of dispersion is within this range, developability tends to be excellent.

The content of the resin (A1) usable in the photosensitive resin composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition. When the content of the resin (A1) is within this range, solubility in a developing solution is sufficient, development residues do not easily occur on the substrate of the non-pixel portion, and film reduction of the pixel portion of the exposed portion occurs well during development And the releasability of the unexposed portions tends to be good.

Examples of the resin (A2) that exhibits alkali solubility and reactivity by the action of at least one of light and heat include (A2-1) to (A2-3).

The resin (A2-1) is a copolymer of (Aa) and (Ab) and a monomer (Ac) having a group having a cyclic ether bond having 2 to 4 carbon atoms .

The resin (A2-2) is a copolymer of (Aa) and (Ab), in which a part of the carboxyl group derived from (Aa) is reacted with a group having a cyclic ether bond having 2 to 4 carbon atoms derived from (Ac) And the like.

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

(Ac) is, for example, a polymerizable compound having at least one group selected from the group consisting of a group having a cyclic ether bond having 2 to 4 carbon atoms (for example, an epoxy group, an oxetanyl group and a tetrahydrofuryl group) . (A-c) is preferably a compound having at least one group selected from the group consisting of groups having a cyclic ether bond having 2 to 4 carbon atoms and having an unsaturated bond.

(A-c) include, for example, a monomer having an epoxy group, a monomer having an oxetanyl group, a monomer having a tetrahydrofuryl group, and the like.

The above-mentioned monomer having an epoxy group means, for example, a polymerizable compound having at least one kind of group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group.

The monomer having an epoxy group is preferably a compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group and having an unsaturated bond.

The aliphatic epoxy group means a group having a structure in which a chain type olefin is epoxidized.

Specific examples of the compound having an aliphatic epoxy group include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, And compounds represented by the following formula (III) described in Japanese Patent Application Laid-Open No. 7-248625.

(In the formula (III), 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 alkyl group include 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, a 1-methyl-n-butyl group, a 1-methyl-n-propyl group, a 1-methyl- , 2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group and cyclohexyl group.

In any of the chemical structural formulas, although it varies depending on the number of carbon atoms, examples of substituents and the like can be similarly applied throughout this specification, unless otherwise specified. In addition, it includes all that can take a linear chain or a branch.

-메틸-o-비닐벤질글리시딜에테르,

-메틸-m-비닐벤질글리시딜에테르,

-메틸-p-비닐벤질글리 시딜에테르, 2,3-디글리시딜옥시메틸스티렌, 2,4-디글리시딜옥시메틸스티렌, 2,5-디글리시딜옥시메틸스티렌, 2,6-디글리시딜옥시메틸스티렌, 2,3,4-트리글리시딜옥시메틸스티렌, 2,3,5-트리글리시딜옥시메틸스티렌, 2,3,6-트리글리시딜옥시메틸스티렌, 3,4,5-트리글리시딜옥시메틸스티렌, 2,4,6-트리글리시딜옥시메틸스티렌 등을 들 수 있다.Examples of the compound represented by the formula (III) include o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,

Methyl-o-vinylbenzyl glycidyl ether,

Methyl-m-vinylbenzyl glycidyl ether,

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

Examples of the monomer having an alicyclic epoxy group include a monomer having an aliphatic monocyclic epoxy group, a monomer having an aliphatic polycyclic epoxy group, and the like.

The alicyclic epoxy group means a group having a structure obtained by epoxidizing a cyclic olefin. The aliphatic monocyclic epoxy group refers to a group having a structure in which a monocyclic cyclic olefin is epoxidized and an aliphatic polycyclic epoxy group means a group having a structure obtained by epoxidizing a cyclic olefin having multiple rings.

The monomer having an aliphatic monocyclic epoxy group means a polymerizable compound having an epoxy group on the ring of the aliphatic monocyclic compound. The monomer having an aliphatic monocyclic epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic monocyclic compound and having an unsaturated bond. The monomer having an epoxy group on the ring of the aliphatic monocyclic compound, and the (meth) acryloyloxy Is more preferable.

Examples of the aliphatic monocyclic compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Among them, a compound having 5 to 7 carbon atoms is preferable.

Specific examples of the monomer having an aliphatic monocyclic epoxy group include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries, Ltd.) 4-epoxycyclohexylmethyl methacrylate (for example, CYROMER A400 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Ltd.) and the like.

The monomer having an aliphatic polycyclic epoxy group means a polymerizable compound having an epoxy group on the ring of the aliphatic polycyclic compound. The monomer having an aliphatic polycyclic type epoxy group is preferably a compound having an epoxy group on the ring of the aliphatic polycyclic type compound and having an unsaturated bond. The monomer having an epoxy group on the ring of the aliphatic polycyclic type compound and having (meth) acryloyloxy Is more preferable.

Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, Tricyclododecane, and the like. Among them, a compound having 8 to 12 carbon atoms is preferable.

Examples of the monomer having an aliphatic polycyclic epoxy group include 3,4-epoxy norbornyl acrylate, 3,4-epoxy norbornyl methacrylate, a compound represented by formula (I) and a compound represented by formula (II) And at least one compound selected from the group consisting of compounds represented by the following general formula (1).

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

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

Specific examples of R ¹ and R ² include a hydrogen atom; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-1-hydroxypropyl group, N-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group, 2-hydroxy- -Butyl group, and the like.

Is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Specific examples of X ¹ and X ² include a single bond; Alkylene groups such as a methylene group, an ethylene group and a propylene group;

Containing alkylene groups such as an alkylene group, an oxyalkylene group, a thioalkylene group and an aminoalkylene group, and specific examples thereof include an oxymethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group , Aminomethylene group, aminoethylene group, aminopropylene group and the like.

Preferably a single bond, a methylene group, an ethylene group, an oxymethylene group and an oxyethylene group, more preferably a single bond and an oxyethylene group.

At least one kind of compound selected from the group consisting of the compound represented by the formula (I) and the compound represented by the formula (II) includes a compound represented by the following formula (I ') and a compound represented by the formula (II' Is preferably at least one kind of compound selected from the group consisting of

In the formulas (I ') and (II'), R ^{1 '} and R ^2' are the same as R ¹ and R ² , respectively.

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

Specific examples of the compound represented by the formula (II) include the compounds represented by the formulas (II-1) to (II-15), preferably the compounds represented by the formulas (II- (II-5), Formula (II-7), Formula (II-9) and Formula (II-11) to Formula (II- , Formula (II-7), formula (II-9), and formula (II-15).

The 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 alone or in combination at any ratio. The mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20:10 to 90:10 in terms of the molar ratio, preferably in the formula (I): formula (II) 80 to 80:20.

The above-mentioned oxetanyl group-containing monomer means, for example, a polymerizable compound having an oxetanyl group. The monomer having an oxetanyl group is preferably a compound having an oxetanyl group and having an unsaturated bond.

Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl- Methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, or 3-methyl- -Ethyl-3-acryloxyethyloxetane and the like.

The above-mentioned monomer having a tetrahydrofuryl group means, for example, a polymerizable compound having a tetrahydrofuryl group. The monomer having a tetrahydrofuryl group is preferably a compound having a tetrahydrofuryl group and having an unsaturated bond.

Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate .

In the resin (A2-1), it is preferable that the proportion of the constituent components derived from each other is in a molar fraction with respect to the total number of moles of constituent components constituting the resin (A2-1), in the following range.

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

(A-b); 1 to 65 mol%

(A-c); 2 to 95 mol%

It is more preferable that the above-mentioned ratio of the constituent components is within the following range.

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

(A-b); 1 to 60 mol%

(A-c); 5 to 80 mol%

When the composition ratio is in this range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

Resin (A2-1) can be produced by the same production method as Resin (A1), except that a compound which derives the units (A-a), (A-b) and (A-c) constituting the copolymer is used.

The resin (A2-2) can be produced through a two-step process. For example, the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972) or in Japanese Patent Application Laid-Open No. 2001-89533 Can be produced by referring to the described method.

First, a resin is obtained in the same manner as the resin (A1) by using a copolymer obtained by copolymerizing (A-a) and (A-b).

In this case, it is preferable that the proportion of the constituent component derived from each of them is in a molar fraction with respect to the total number of moles of constituent components constituting the above-mentioned copolymer, in the following range.

A structural unit derived from the structural unit (A-a); 5 to 50 mol%

(A-b); 50 to 95 mol%

It is more preferable that the above-mentioned ratio of the constituent components is within the following range.

A structural unit derived from the structural unit (A-a); 10 to 45 mol%

(A-b); 55 to 90 mol%

The weight average molecular weight and the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the obtained resin in terms of polystyrene may be the same as that of the resin (A1).

Next, a part of the carboxylic acid and carboxylic acid anhydride (Aa) derived from the copolymer obtained by copolymerizing (Aa) and (Ab) is reacted with (Ac) Oxetanyl group or tetrahydrofuryl group, which is derived from the reaction product.

Subsequently, the atmosphere in the flask is replaced with air with nitrogen, and the component (Ac), the reaction catalyst and the polymerization inhibitor are placed in a flask and reacted at 60 to 130 ° C for 1 to 10 hours Lt; / RTI >

In addition, as in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facilities and the amount of heat generated by polymerization.

(A-c) is usually 5 to 80 mol%, preferably 10 to 75 mol%, and more preferably 15 to 70 mol% based on the molar amount of (A-a). When the composition ratio is within this range, balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be improved.

The reaction catalyst is suitably used, for example, as a reaction catalyst with a carboxyl group, an epoxy group, an oxetanyl group or a tetrahydrofuryl group. Specific examples thereof include trisdimethylaminomethylphenol and the like.

The amount of the reaction catalyst used in this case is usually about 0.001 to 5% by mass based on the total amount of the monomers (A-a) to (A-c).

The polymerization inhibitor may be exemplified by hydroquinone.

The amount of the polymerization inhibitor to be used is usually about 0.001 to 5% by mass based on the total amount of the monomers (A-a) to (A-c).

The resin (A2-3) can be produced by the same production method as that of the resin (A1), except that a compound which derives the units (A-a) and (A-c) constituting the copolymer is used.

In the resin (A2-3), it is preferable that the proportion of the constituent component derived from each of the resins (A2-3) falls within the following range in mole fraction with respect to the total number of moles of the constituent components constituting the resin (A2-3).

A structural unit derived from the structural unit (A-a); 5 to 95 mol%

(A-c); 5 to 95 mol%

It is more preferable that the above-mentioned ratio of the constituent components is within the following range.

A structural unit derived from the structural unit (A-a); 10 to 90 mol%

(A-c); 10 to 90 mol%

When the composition ratio is in this range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be improved.

Examples of the polymerizable monomer (B) contained in the photosensitive resin composition of the present invention include monofunctional monomers, bifunctional monomers, and multifunctional monomers having three or more functionalities.

Examples of the monofunctional monomer include nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- ethylhexylcarbitol (meth) acrylate, 2- Acrylate, stearyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone (Meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate or N-vinylpyrrolidone.

Examples of the bifunctional monomer include 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, (Acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate or 3-methylpentanediol Di (meth) acrylate, and the like.

Examples of multifunctional monomers having three or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethyl (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, Pentaerythritol tri (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, dipentaerythritol penta (Meth) acrylate, caprolactone-modified caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified Caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone- Acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone (Meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, or Caprolactone-modified tripentaerythritol (meth) acrylate and acid anhydride.

In the present specification, caprolactone denaturation means that a caprolactone ring-opening polymer or ring opening polymer is introduced between the alcohol-derived site of the (meth) acrylate compound and the (meth) acryloyloxy group.

Among them, it is preferable to use a bifunctional or higher polyfunctional monomer.

The content of the polymerizable monomer (B) is preferably 1 to 70% by mass, more preferably 5 to 60% by mass, based on the total amount of the resin (A) and the polymerizable monomer (B). When the content of the polymerizable monomer (B) is within this range, the strength, smoothness, reliability and mechanical strength of the coating film and pattern tend to be good.

The photosensitive resin composition of the present invention may further contain at least one compound (Y) selected from the group consisting of a compound having a carboxylic acid anhydride and at least two carboxyl groups. Examples of the latter compound include polycarboxylic acid anhydrides and polycarboxylic acids.

As the carboxylic acid anhydride, an epoxy resin curing agent comprising a commercially available colorless acid anhydride can be preferably used. Concretely, there are listed Adeka Hardener EH-700 (trade name, hereinafter the same), Asahi Denka Kogyo Co., Ltd., Recascit HH, Copper MH-700 (manufactured by Shin-Etsu Chemical Co., Ltd.) 126, copper YH-306, copper DX-126 (manufactured by Yucca Shell Epoxy Co., Ltd.), and the like.

As the polycarboxylic acid anhydride, for example,

Anhydrous tricarballylic acid, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornenedicarboxylic acid, anhydrous hymic acid, and the like can be used as the acid anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, Aliphatic dicarboxylic acid anhydride;

Aliphatic polycarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride and cyclopentanetetracarboxylic acid dianhydride;

Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride;

And ester group-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tris trimellitate.

Among them, phthalic anhydride and trimellitic anhydride are preferable in view of high transparency and high resolution.

As the polycarboxylic acid, for example,

Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid;

Cycloaliphatic polycarboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanecarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid;

Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid and benzophenonetetracarboxylic acid.

Among them, phthalic acid and trimellitic acid are preferable in view of high transparency and high resolution.

The content of the compound (Y) in the photosensitive resin composition of the present invention is preferably from 0.1 to 20% by mass, more preferably from 1 to 20% by mass with respect to the total amount of the binder resin (A) and the polymerizable monomer (B) To 15% by mass. When the compound (Y) is in this range, the resolution and the residual film ratio can be improved.

Examples of the polymerization initiator (C) contained in the photosensitive resin composition of the present invention include compounds that initiate polymerization by the action of light or heat, and examples thereof include a nonimidazole compound, an acetophenone compound, a triazine compound , Acylphosphine oxide-based compounds or oxime-based compounds. Among them, a nonimidazole-based compound is preferable because of its excellent sensitivity.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- 4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373 and the like), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'- (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Unexamined Patent Publication No. 62-174204, Imidazole compounds in which the phenyl group at the 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-7-10913).

Preferred are 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- (2-hydroxyethoxy ) Phenyl] -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2- 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino 1- (4-morpholinophenyl) -butanone, 2- (3-methylphenyl) butan- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- , 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-di (4-morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethyl 2- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) -2-dimethylamino- (4-morpholinophenyl) -butanone, 2- (2-methoxybenzyl) -2-dimethylamino-1- Butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxybenzyl) -4- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino- 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

Examples of the triazine compound include 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- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

Examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

-옥시이미노-1-페닐프로판-1-온, 식 (1) 로 나타내는 화합물, 식 (2) 로 나타내는 화합물 등을 들 수 있다.Examples of the oxime compound include O-ethoxycarbonyl-

-Oxyimino-1-phenylpropan-1-one, a compound represented by formula (1) and a compound represented by formula (2).

The polymerization initiator (C) of the photosensitive resin composition of the present invention may contain the following photopolymerization initiator and the like.

Examples of the photopolymerization initiator include benzoin-based compounds, benzophenone-based compounds, and thioxanthone-based compounds.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro- -Propoxyloxanthone, and the like.

Further, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate or a titanocene compound may be used as a photopolymerization initiator.

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

Examples of the photopolymerization initiator having a group capable of causing chain transfer include the photopolymerization initiators represented by the following formulas (3) to (8).

Further, an optical and / or thermal cationic polymerization initiator may be used.

As the optical and / or thermal cation polymerization initiator, those composed of onium cation and anions derived from Lewis acid may also be used.

Specific examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis Iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) Tris (p-tolyl) sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6- (Methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (p-chlorophenyl) sulfonium, (Octadecoxy) sulfonium, dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium , Dimethyl (cyclohexyl (3-bromoproxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, Dimethyl (2-hydroxyisopropoxy) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium And the like.

Preferable examples of the onium cation include bis (p-tolyl) iodonium, p-tolyl (p-isopropylphenyl) iodonium, bis -tert-butylphenyl) sulfonium, and the like.

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

These onium cation and anions derived from Lewis acid can be arbitrarily combined.

Specific examples of the cation polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis Iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, bis (P-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, pentaerythritol hexafluorophosphate, pentaerythritol hexafluorophosphate, , Ethyl naphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexa (P-tert-butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, p-cyanophenylsulfonium hexafluorophosphate, , Tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl ), Dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl Sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (Pentafluoroethoxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (3-bromoproxy) sulfonium hexafluorophosphate, dimethyl (Trichloromethyl) methylsulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate, Phosphate;

Diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis ), Iodonium hexafluoroarsenate, bis (p-octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate (p-phenylphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, , Methyl naphthyl iodonium hexafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate , Tris (p-isopropylphenyl) sulfonium hexafluoro Tris (2,6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexa Dimethyl (methoxy) hexafluoroarsenate, dimethyl naphthylsulfonium hexafluoroarsenate, diethyl naphthylsulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate, (Methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate , Dimethyl (octyloxy) sulfonium hexafluoroarsenate, dimethyl (octadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl Ethoxy) sulfonium hexafluoro Dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) sulfonium hexafluoroarsenate, dimethyl (fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) Tetra (trichloromethyl) methyl) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroarsenate;

Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis ), Iodonium hexafluoroantimonate, bis (p-octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis Iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate , Methylnaphthyl iodonium hexafluoroantimonate, ethylnaphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate , Tris (p-isopropylphenyl) sulfonium hexafluoro (P-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium (P-chlorophenyl) sulfonium hexafluoroantimonate, dimethylnaphthylsulfonium hexafluoroantimonate, diethylnaphthylsulfonium hexafluoroantimonate, dimethyl (methoxy ) Sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate (Octadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (octyloxy) sulfonium hexafluoroantimonate, dimethyl Butoxy) sulfonium hexafluoro Dimethyl (cyclopentyloxy) sulfonium hexafluoroantimonate, dimethyl (cyclohexyloxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroantimonate , Dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecaneoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) Tetra (trichloromethyl) methyl) sulfonium hexafluoroantimonate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoroantimonate;

(Pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert- butylphenyl) iodonium tetrakis ) Borate, bis (p-octylphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) Iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) (Pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethyl naphthyl iodonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, (Pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) sulfonium tetrakis Borate, tris (2,6-dimethylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-tert- butylphenyl) sulfonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, tris (p-chlorophenyl) sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis ) Sulfonium tet (Pentafluorophenyl) borate, dimethyl (octyldecyloxy) borate, dimethyl (octyldecyloxy) borate, dibutyldodecyl (Pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (fluoromethoxy) sulfonium tetrakis (pentafluorophenyl) ) Borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromoproxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) methylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis Borate, and the like.

Preferable examples include iodonium hexafluorophosphate such as bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p- (P-tolyl) (p-tolyl) pentaerythritol hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (P-tert-butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) sulfonium iodonium hexafluoroarsenate, (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, Phenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoro (P-tolyl) (p-isopropylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) ), Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) Tetrakis (pentafluorophenyl) borate, and the like.

More preferred examples thereof include bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (P-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentaerythritol hexafluoroantimonate), triphenylsulfonium hexafluoroantimonate, Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, , Triphenylsulfonium tetrakis (pentafluorophenyl) borate, and tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

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

When the content of the polymerization initiator (C) is within this range, the sensitivity of the photosensitive resin composition becomes high, and the strength of the coating film or pattern formed by using the photosensitive resin composition described above and the smoothness on the surface of the coating film or pattern Tends to be improved.

In the photosensitive resin composition of the present invention, the polymerization initiator (C-1) may be used in combination with the polymerization initiator (C) so as not to impair the effect of the present invention.

Examples of the polymerization initiation aid (C-1) include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, compounds represented by formula (IV), and compounds represented by formula (V) or formula (VI).

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine; aliphatic amine compounds such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (Ethylhexyl) benzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- And aromatic amines such as benzophenone.

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

A polyfunctional thiol compound is a compound having two or more sulfanyl groups in a molecule.

Specific examples of the polyfunctional thiol compound include hexane dithiol, decanediol, 1,4-dimethyl mercaptobenzene, butanediol bis-thiourethionate, butanediol bis-thioglycolate, ethylene glycol bis-thioglycolate, trimethylolpropane tris Thioglycolate, butanediol bis-thiophosphate, trimethylolpropane tristhiopropionate, trimethylolpropane tris thioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxy Pentaerythritol tetrakis (3-mercaptobutyrate) or 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

Among them, a compound having two or more sulfanyl groups bonded to the carbon atoms of the aliphatic hydrocarbon group is more preferable because the sensitivity of the photosensitive resin composition of the present invention is high.

The compound represented by the formula (IV) is the following compound.

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

Y represents an oxygen atom 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 with a halogen atom or an aryl group which may be substituted with 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 benzene rings, methylbenzene rings, dimethylbenzene rings, ethylbenzene rings, propylbenzene rings, butylbenzene rings, pentylbenzene rings, hexylbenzene rings, cyclohexylbenzene rings, chlorobenzene rings, Benzene ring, bromobenzene ring, dibromobenzene ring, phenylbenzene ring, chlorophenylbenzene ring, bromophenylbenzene ring, naphthalene ring, chloronaphthalene ring, bromonaphthalene ring, phenanthrene ring, A lanthylene ring, a benzo [a] pyrene ring, a benzo [e] pyrene ring, a perylene ring and derivatives thereof. Among them, a benzene ring, a naphthalene ring and the like are preferable.

Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include a benzene ring, a methylbenzene ring, a dimethylbenzene ring, an ethylbenzene ring, a propylbenzene ring, a butylbenzene ring, a pentylbenzene ring, a hexylbenzene ring, a cyclohexylbenzene ring , A chlorobenzene ring, a dichlorobenzene ring, a bromobenzene ring, a dibromobenzene ring, a phenylbenzene ring, a chlorophenylbenzene ring, a bromophenylbenzene ring, a naphthalene ring, a chloronaphthalene ring, a bromonaphthalene ring, etc. have.

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl- Butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl- Propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group and the like.

Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl- butyl group, 1-methyl-n-butyl group, 1-methyl-n-butyl group, Dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, an n-hexyl group, a cyclohexyl group, n-butyl group, and the like.

Examples of the aryl group which may be substituted with a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobenzophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, a bromophenyl group, A phenyl group, a naphthyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonaphthyl group.

As the compound represented by the formula (IV), specifically,

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Among them, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the formula (9), 2-benzoylmethylene-3-methyl-naphtho [1,2-d ] Thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the formula (11) are preferable.

The compounds represented by the formulas (V) and (VI) are the following compounds.

In the formulas (V) and (VI), the rings X ³¹ and 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 aryl group having 6 to 12 carbon atoms.

The carbon atoms contained in these aromatic rings, alkyl groups or aryl groups may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and the hydrogen atoms contained in these aromatic rings, alkyl groups or aryl groups may be substituted with halogen atoms. The hydrogen atom contained in the aryl group may be substituted with a hydroxyl group or an alkoxy group.

Examples of the hydroxyl-substituted aryl group include a hydroxyphenyl group and a hydroxynaphthyl group.

Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms. Specific examples thereof include methoxy, ethoxy, propoxy and butoxy.

Examples of the alkoxy group-substituted aryl group include methoxyphenyl, ethoxyphenyl, propoxyphenyl, methoxynaphthyl, ethoxynaphthyl, propoxynaphthyl and the like.

As the compound represented by the formula (V) or the formula (VI), specifically,

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

But are not limited to, dimethoxyanthracene, dimethoxyanthracene, diethoxyanthracene, dipropoxyanthracene, diisopropoxyanthracene, dibutoxyanthracene, dipentaoxyanthracene, dihexaooxyanthracene, methoxyethoxyanthracene, methoxypropoxyanthracene, methoxyisopropoxy Examples of the alkoxy include alkoxy groups such as anthracene, methoxybutoxyanthracene, ethoxypropoxyanthracene, ethoxyisopropoxyanthracene, ethoxybutoxyanthracene, propoxyisopropoxyanthracene, propoxybutoxyanthracene, isopropoxybutoxyanthracene, Anthracene,

And dialkoxynaphthacenes such as dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene, dibutoxynaphthacene, and the like.

The content of the polymerization initiator (C-1) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40% by mass, based on the total amount of the resin (A) and the polymerizable monomer (B).

Particularly when a polyfunctional thiol compound is used as the polymerization initiator (C-1), the content thereof is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, based on the polymerization initiator (C) 15% by mass.

The content of the compound represented by at least one kind selected from the group consisting of the formulas (V) and (VI) is preferably 50 to 100% by mass, more preferably 50 to 100% by mass with respect to the content of the polymerization initiator (C- Is 60 to 100% by mass, and more preferably 65 to 100% by mass. When the content of these compounds is within this range, transparency of the coating film is favorable when a coating film is formed using the photosensitive resin composition containing the compound.

When the amount of the polymerization initiator (C-1) is within the above range, the sensitivity of the resulting photosensitive resin composition becomes higher, the developing property becomes better, and the productivity of the pattern formed using the photosensitive resin composition tends to be improved have.

The photosensitive resin composition of the present invention contains a solvent (D). Examples of the solvent (D) include various organic solvents used in the field of the photosensitive resin composition.

Specific examples include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

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

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

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

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

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

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

Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate, and the like:

Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate;

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

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

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

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

Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxypropionate, methylhydroxyacetate, , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, propoxy ethyl acetate, propoxy propyl acetate, propoxy propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, Methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, , Propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, 3-butoxypropionic acid ethyl, 3-propoxypropionate, Esters such as ropil, 3-butoxy-propionic acid butyl;

Cyclic ethers such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone.

The above-mentioned solvent (D) contains a solvent having a boiling point of 140 占 폚 or more and 175 占 폚 or less from the viewpoint of coatability and drying property. As the solvent having a boiling point of 175 占 폚 or less, alkylene glycol alkyl ether acetates; Alcohols such as methoxybutanol and ethoxybutanol; ketones such as cyclohexanone; Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxyacetate, butyl 3-methoxyacetate, and butyl 3-ethoxyacetate, and preferably methoxybutanol , Methoxybutyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate.

These solvents (D) may be used alone or in combination of two or more, preferably two or more. The solvent (D) may have a boiling point exceeding 175 캜.

It is preferable that the solvent (D) contains an alcohol having 1 to 6 carbon atoms. These alcohols can be appropriately selected from the above-mentioned solvents. Such an alcohol preferably has a boiling point of 175 캜 or lower, but may have a boiling point of 175 캜 or higher.

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 60 to 90% by mass, more preferably 65 to 85% by mass, based on the mass of the photosensitive resin composition. When the content of the solvent (D) is within this range, the coating property is improved when the coating liquid is applied by various coating apparatuses described later. When a solvent having a boiling point exceeding 175 캜 is contained, such a solvent is preferably contained in an amount of about 30% by mass or less in the total solvent.

The surfactant (E) in the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom. Among them, silicone surfactants having fluorine atoms are preferred. By using such a surfactant (E), it is possible to prevent the generation of minute bubbles contained in the composition, in addition to other components and the content thereof in the photosensitive resin composition. As a result, it is possible to effectively suppress the Dolby during evaporation of the solvent.

As the silicone surfactant, a surfactant having a siloxane bond can be mentioned. Concretely, it is possible to use a silicone resin such as Tororensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether Modified Silicone Oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, (Manufactured by Shin-Etsu Silicones), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.).

As the fluorine-based surfactant, a surfactant having a fluorocarbon chain can be mentioned. More specifically, Furorinato (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper R30 (Manufactured by Dainippon Ink and Chemicals, Inc.), EFTAX (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by Shin Akita Chemical Co., Ltd.), Sufuron (registered trademark) S381, S382, , SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratories), BM-1000 and BM-1100 (both trade names: manufactured by BM Chemie).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477, Copolymer F443 (manufactured by Dainippon Ink and Chemicals, Inc.). And preferably Megapack (registered trademark) F475.

The surfactant (E) is usually 0.0025 to 0.0250 mass%, preferably 0.0025 to 0.0200 mass%, more preferably 0.05 to 0.0100 mass%, based on 100 mass% of the photosensitive resin composition excluding the surfactant. By containing the surfactant in this range, the flatness can be improved, and the dolbid can be effectively prevented as described above.

Additives such as a filler, a polymer compound other than the resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, an aggregation inhibitor and a chain transfer agent may be used in combination in the photosensitive resin composition of the present invention.

It is preferable that the photosensitive resin composition of the present invention contains substantially no coloring agent such as pigment and dye. In short, in the photosensitive resin composition of the present invention, the content of the colorant in the total composition is preferably less than 1% by mass, and more preferably less than 0.5% by mass.

Examples of the filler include glass, silica and alumina.

Examples of the polymer compound other than the resin (A) include a curable resin such as an epoxy resin and a maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, And the like.

The adhesion promoter is preferably a silane-based compound. Specific examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Ethoxy silane, and the like.

Examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4- methylphenyl acrylate, 2- [1- Butylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 6- [3- (3- tert- 2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- (3- Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert 4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert- butyl- , 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3'-thiodipropionate, pentaerythrityl tetrakis rock Benzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5' Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3- 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- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy- Butyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- Methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (3-tert- butyl-2-hydroxy- ) -5-chlorobenzotriazole or alkoxybenzophenone, and the like.

Examples of the light stabilizer include a polymer comprising succinic acid and (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) ethanol, N, N ', N " Tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) triazin- (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydroxy (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1,1-dimethylethyl) -4- hydroxyphenyl] methyl ] Butyl malonate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- -Hydroxyethylamine) -1,3,5-triazine, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate or methyl (1,2,2,6,6- Pentamethyl-4-piperidinyl) sebacate, and the like.

Examples of the anti-aggregation agent include sodium polyacrylate and the like.

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

The photosensitive resin composition of the present invention preferably has a solid content of about 10 to 30% by weight, more preferably 12 to 28% by weight, and still more preferably 15 to 25% by weight. By setting this range, it is possible to form a uniform coating film without causing defects or cloudy unevenness by various coating methods, particularly slit method.

When the photosensitive resin composition of the present invention is packed in a quartz cell having an optical path length of 1 cm and the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm, the transmittance is usually 70% or more, Is more than 80%.

When the photosensitive resin composition of the present invention is used as a coating film, the transmittance of the coating film is preferably 90% or more, more preferably 95% or more. The transmittance was measured with a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm for a coating film having a thickness of 3 占 퐉 after heat curing (for example, 100 to 250 占 폚 for 5 minutes to 3 hours) Value. Thus, a coating film excellent in transparency can be provided.

The photosensitive resin composition of the present invention may, for example, be a base material; Substrates such as glass, metal, and plastic; A color filter, various insulating or conductive films, a driving circuit, and the like formed thereon. The coated film is preferably dried and cured. The obtained coating film may be patterned into a desired shape and used as a pattern. These coating films or patterns may be formed as a part of constituent parts such as a display device.

First, the photosensitive resin composition of the present invention is applied onto a substrate or a layer comprising a solid content of the photosensitive resin composition formed as described above.

The coating method is not particularly limited, and a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater or a curtain flow coater), an inkjet, a roll coater, . Among them, it is preferable to use a slit coating method, that is, a slit & spin coater, a slit coater or the like, in view of solubility, prevention of drying, prevention of generation of foreign matter,

Subsequently, it is preferable to remove the volatile components such as a solvent by drying or prebaking. Thus, a smooth uncured coating film can be obtained. In particular, it is preferable to carry out drying under reduced pressure. Here, the reduced-pressure drying is to be carried out by removing at least a part of the solvent to such an extent as not to be an obstacle in the subsequent process, and it is not necessarily required to remove all the solvent from the coating film. The reduced pressure drying is preferably carried out at a room temperature (25 ° C) under an atmospheric pressure to an ultimate pressure of 10 to 500 Pa, more preferably 30 to 400 Pa, still more preferably 50 to 300 Pa. There is no limitation on the decompression drying time, and it can be suitably set in consideration of the film thickness, the size of the substrate, the amount of the solvent of the photosensitive resin composition, and the like. And it is usually between 10 seconds and 60 seconds. In order to apply such a comparatively stringent vacuum drying condition, the pressure reduction rate may be changed in multiple stages until the final reached pressure is reached. For example, a smoother uncured film can be obtained by controlling the decompression speed in two steps from about 10 seconds to about 130 Pa at normal pressure and about 10 seconds from about 130 Pa to about 66 Pa.

The film thickness of the coating film in this case is not particularly limited and can be suitably adjusted in accordance with the materials to be used and applications and is usually about 0.1 to 30 μm, preferably about 1 to 20 μm, more preferably about 1 to 6 μm .

Then, light, for example, ultraviolet rays generated in a mercury lamp, a light emitting diode, or the like is irradiated to the obtained uncured coating film through a mask for forming a desired pattern. The shape of the mask at this time is not particularly limited, and various shapes can be cited. In addition, the line width and the like can be appropriately adjusted in accordance with the mask size and the like.

In recent exposures, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or light having wavelengths around 436 nm, around 408 nm, and around 365 nm is extracted by a bandpass filter So that it is possible to uniformly irradiate the entire exposed surface with a parallel light beam. In this case, a device such as a mask aligner or a stepper may be used to accurately align the mask and the substrate.

Thereafter, a desired pattern shape can be obtained by bringing the coating film into contact with an aqueous alkali solution to dissolve and develop a predetermined portion, for example, an unexposed portion.

The developing method may be any of a liquid mounting method, a dipping method, and a spraying method. Also, the base material may be inclined at an arbitrary angle during development.

The developing solution used for development is usually an aqueous solution containing an alkaline compound and a surfactant.

The alkaline compound may be either an inorganic or an organic alkaline compound.

Examples of the inorganic alkaline compound include inorganic bases such as sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, potassium carbonate, sodium hydrogencarbonate , Potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropyl Amine, diisopropylamine, ethanolamine, and the like.

The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of nonionic surfactants, anionic surfactants or cationic surfactants.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like.

Examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium lauryl sulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate and dodecylnaphthalene And alkylarylsulfonic acid salts such as sodium sulfonate.

Examples of cationic surfactants include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10 mass%, more preferably 0.05 to 8 mass%, and still more preferably 0.1 to 5 mass%.

After development, it may be washed with water and post-baked if necessary. Post bake is suitable for temperature range of 150 ~ 230 ℃ for 10 ~ 180 minutes.

In particular, the photosensitive resin composition of the present invention is preferably used for producing a coating film by applying a photosensitive resin composition of the present invention on a substrate using a slit coater to form a film, and drying the film formed on the substrate under reduced pressure.

It is also preferable to use the obtained coating film for the purpose of producing a pattern by exposing through a photomask and developing the exposed coating film.

The coating film or pattern thus obtained is useful as, for example, a photo-spacer used in a liquid crystal display device, a patternable overcoat. In addition, holes can be formed by using a photomask for hole formation during patterning exposure of an uncured overcoat film, which is useful as an interlayer insulating film. Then, at the time of exposure to the uncured coating film, the transparent film can be formed by performing only the entire surface exposure and heat curing or heat curing without using a photomask. This transparent film is useful as an overcoat. It can also be used in a display device such as a touch panel. Thus, it is possible to manufacture a display device having a high-quality coating film or pattern at a high yield.

The photosensitive resin composition of the present invention can be used for forming various films and patterns, for example, a transparent film, a transparent film constituting a part of a color filter, a pattern, a photo spacer, an overcoat, , A microlens, a coloring pattern combined with a different film thickness, a coat layer, and the like. Further, a color filter, an array substrate, and the like having these coating films or patterns as a part of their constituent parts and further display devices including such color filters and / or array substrates, for example, liquid crystal display devices, Can be used.

According to the photosensitive resin composition of the present invention, it is possible to suppress the occurrence of defects and cloudiness caused by the spin ratio of the solvent, and to form a uniform and high quality coating film over the entire coating film.

Further, by using such a photosensitive resin composition, a high-quality display device can be obtained.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples and comparative examples,% and parts representing the content or amount are based on mass unless otherwise specified.

Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added , And the mixture was heated to 70 DEG C while stirring.

Subsequently, 60 parts by mass of methacrylic acid, a mixture of a compound represented by the formula (I-1) and a compound represented by the formula (II-1), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate Mole ratio = 50: 50) was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution.

The obtained solution was dropped into a flask kept at 70 캜 for 4 hours using a dropping funnel.

On the other hand, a solution prepared by dissolving 45 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts by weight of 3-methoxybutyl acetate was added to the flask over 4 hours using another dropping funnel .

After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a resin solution of a copolymer (resin Aa) having a solid content of 32.3% by mass and an acid value of 35.6 mg-KOH / g . The weight average molecular weight (Mw) of the obtained resin Aa was 9.1 × 10 ³ and the degree of dispersion was 2.02.

Synthesis Example 2

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

Next, a mixture of 40 parts by mass of methacrylic acid, 3,4-epoxytricyclo [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) was dissolved in 190 parts by mass of diethylene glycol ethyl methyl ether to prepare a solution.

The obtained solution was dropped into a flask maintained at 70 캜 for 4 hours by using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 240 parts by mass of diethylene glycol ethyl methyl ether was charged into a flask .

After completion of the dropwise addition of the polymerization initiator solution, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 42.6 mass% and an acid value of 60 mg-KOH / g. The weight average molecular weight (Mw) of the obtained resin Ab was 8.0 × 10 ³ and the degree of dispersion was 1.91.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder polymer was carried out under the following conditions using the GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

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

Examples 1 to 8 and Comparative Examples 1 to 3

Each component was mixed with the composition shown in Table 1 to obtain a photosensitive resin composition.

In Table 1,

Polymerizable monomers (B); Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

A polymerization initiator (C); 2-methyl-1- (4-methylsulfanylphenyl) -2-morpholinopropane-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals)

Solvent (Da); 3-methoxy-1-butanol (boiling point 161 DEG C)

Solvent (Db); Ethyl 3-ethoxypropionate (boiling point 170 ° C)

Solvent (Dc); 3-methoxybutyl acetate (boiling point 171 DEG C)

Solvent (Dd); Diethylene glycol ethyl methyl ether (boiling point 176 ° C)

Solvent (De); Propylene glycol monomethyl ether acetate (boiling point 146 DEG C)

Solvent (Df); Benzyl alcohol (boiling point 205 占 폚)

Solvent (Dg); Ethylene glycol monobutyl ether acetate (boiling point: 192 DEG C)

Surfactant (E); Polyether-modified silicone oil (SH8400 manufactured by Toray Dow Corning Co., Ltd.).

The solvent (D) is mixed such that the solid content of the composition is the "solid content (%)" in Table 1, and the value of the solvent component in the solvent (D) represents the mass ratio in the solvent (D). The content of the surfactant (E) represents the mass ratio to the photosensitive resin composition excluding the surfactant of 100 mass%.

≪ Evaluation of Dolby and haze stains >

The composition solution prepared on the ITO film-formed glass substrate of 15 cm in length and 15 cm was applied using a slit die coater (Takeda-100, manufactured by Itochu Co., Ltd.) under the condition that the film thickness after curing became 3.0 탆. Thereafter, the reduced pressure was reduced to a pressure of 0.5 torr with a vacuum dryer (VCD Microtech Co., Ltd.), followed by drying and further baking on a hot plate at 90 캜 for 2 minutes to form a coating film A.

The resultant coating film A was cooled, and its surface was irradiated with a Na lamp to visually confirm the surface of the coating film.

When the defect caused by Dolby was clearly confirmed, it was indicated by X, when it was barely confirmed, and when it was hardly confirmed, it was indicated by.

When it was possible to clearly identify cloudiness, it was determined as " C ", when it was barely confirmed, " DELTA, "

<Evaluation of Uniformity>

The film thickness of the obtained coating film A was measured at a measurement point at which the distance from the end portion within 12.5 mm was aligned on the matrix at intervals of 12.5 mm. The maximum film thickness, the minimum film thickness and the average film thickness were determined and evaluated by the formula (1).

Uniformity (%) = (maximum film thickness x minimum film thickness) / (2 x average film thickness) x 100 (1)

A case where the uniformity was less than 3%, a case where the uniformity was less than 3%, a case where the ratio was 3 to 5%, and a case where the uniformity was 5% or more.

<Evaluation of Decompression Drying Time>

On the ITO film-formed glass substrate of 15 cm in length and 15 cm, the prepared composition solution was applied using a slit die coater (Takeda-100, manufactured by Itochu Kagaku Co., Ltd.) under the condition that the film thickness after curing became 3.0 탆. Thereafter, under the conditions of a rotary pump revolution of 1800 rpm, a booster pump revolution of 3600 rpm, and a room temperature of 25 DEG C, the time until the reduced pressure reached 66 Pa (hereinafter referred to as &quot; VCD time).

The shorter the VCD time is, the better.

[Industrial applicability]

The photosensitive resin composition of the present invention can uniformly spread over the entire surface of a large area and also suppresses occurrence of defects and cloudiness caused by the dolvite of the solvent. Further, it is possible to form a pattern having high resolution and a high transmittance. Therefore, it can be suitably used for forming coating films and patterns used in display devices such as overcoat, photo spacers, insulating films, projections for controlling liquid crystal alignment, and coat layers for adjusting the film thickness of colored patterns.

Claims (9)

1. A photosensitive resin composition comprising a resin (A), a polymerizable monomer (B), a polymerization initiator (C), a solvent (D) and a surfactant (E) The resin (A) contains at least one (Aa) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a monomer (Ab) copolymerizable with the (Aa) , A resin (A2-1) which is a copolymer of a monomer (Ac) having a group having a cyclic ether bond having 2 to 4 carbon atoms, and (A2-3) which is a copolymer of at least one monomer (A-a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a monomer (A-c) having a group having a cyclic ether bond having 2 to 4 carbon atoms, And at least one kind selected from the group consisting of (A-c) is a monomer containing a polymerizable compound having an alicyclic epoxy group on the ring of the aliphatic monocyclic compound or on the ring of the aliphatic polycyclic compound, The solvent (D) is a solvent containing two or more kinds of solvents having a boiling point of 140 占 폚 or more and 175 占 폚 or less, The content of the surfactant (E) is 0.0025 to 0.0250% by weight based on 100% by weight of the photosensitive resin composition excluding the surfactant, And a solid content of 10 to 30% by weight. delete The method according to claim 1, Wherein the solvent (D) is a solvent containing an alcohol having 1 to 6 carbon atoms. The method according to claim 1, Wherein the solvent (D) is a solvent containing 3-methoxybutanol. The method according to claim 1, Wherein the surfactant (E) is at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom. A coating film formed using the photosensitive resin composition according to claim 1. A pattern formed by using the photosensitive resin composition according to claim 1. A display device comprising the coating film according to claim 6. A display device comprising the pattern according to claim 7.