KR101715392B1 - Photosensitive resin composition - Google Patents

Abstract

At least one compound (B) selected from the group consisting of a binder resin (A), a carboxylic acid anhydride and a compound having at least two carboxyl groups, a photopolymerizable compound (C), and a photopolymerization initiator (D)

Wherein the binder resin (A) comprises at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) copolymerizable with the (Aa) And a monomer (Ac) having an ether group is polymerized with at least one kind of monomer.

Description

[0001] PHOTOSENSITIVE RESIN COMPOSITION [0002]

The present invention relates to a photosensitive resin composition.

It is proposed that a spacer (photo-spacer) is formed by photolithography using a photosensitive resin composition between a color filter and an array substrate constituting a display device such as a liquid crystal display device or a touch panel. According to this method, a spacer can be formed at an arbitrary place.

As such a photosensitive resin composition, there is known a resin composition containing a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent which are copolymerized with an unsaturated carboxylic acid and / or an unsaturated carboxylic anhydride and an aliphatic polycyclic epoxy compound (Patent Document 1 ).

[Patent Document 1] Japanese Patent Laid-Open No. 2008-181087

However, in the above-mentioned photosensitive resin composition, the resolution of the obtained pattern was not sufficient.

It is an object of the present invention to provide a photosensitive resin composition capable of forming a pattern with a high transmittance exhibiting a sufficient resolution.

The present inventors have found that when an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa) is polymerized with a monomer (Ab) copolymerizable with (Aa) and / or a monomer (Ac) having a cyclic ether group having 2 to 4 carbon atoms, A photosensitive resin composition comprising a binder resin (A), a photopolymerizable compound (C) and a photopolymerization initiator (D) comprising at least one carboxyl group selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups It has been found that the resolution of the pattern obtained by using the compound (B) of the species is improved.

That is, the present invention provides the following [1] to [11].

[One]. At least one compound (B) selected from the group consisting of a binder resin (A), a carboxylic acid anhydride and a compound having at least two carboxyl groups, a photopolymerizable compound (C), and a photopolymerization initiator (D)

Wherein the binder resin (A) contains at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) copolymerizable with the (Aa) And a monomer (Ac) having a cyclic ether group is polymerized with at least one monomer selected from the group consisting of a monomer having a cyclic ether group (Ac).

[2]. Wherein the binder resin (A) is a copolymer obtained by polymerizing at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa) and a monomer (Ac) having a cyclic ether group having 2 to 4 carbon atoms The photosensitive resin composition according to [1], which is a binder resin.

[3]. The photosensitive resin composition according to [1] or [2], wherein the monomer (A-c) having a cyclic ether group having 2 to 4 carbon atoms is a monomer having an epoxy group.

[4]. The photosensitive resin composition according to [3], wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group.

[5] The photosensitive resin composition according to [4], wherein the monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II).

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

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

[6]. At least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid, an aliphatic unsaturated carboxylic acid anhydride, or an aliphatic unsaturated carboxylic acid and an aliphatic unsaturated carboxyl The photosensitive resin composition according to any one of [1] to [5], which is an acid anhydride.

[7]. At least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is selected from the group consisting of the compound represented by formula (I ') and the compound represented by formula (II' Is at least one kind of compound selected from the group consisting of compounds represented by the following general formulas (1) and (2).

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

[8]. The photosensitive resin composition according to any one of [1] to [7], wherein the at least one compound (B) selected from the group consisting of a carboxylic acid anhydride and a compound having at least two carboxyl groups is a carboxylic acid anhydride.

[9]. Use of the light-sensitive resin composition according to any one of [1] to [8] for forming a coating film or a pattern.

[10]. A coating film or pattern formed using the photosensitive resin composition according to any one of [1] to [8].

[11]. A display device comprising the coating film or the pattern described in [10].

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition of the present invention comprises at least one compound (B) selected from the group consisting of a binder resin (A), a carboxylic acid anhydride and a compound having at least two carboxyl groups, a photopolymerizable compound (C) (D)

Wherein the binder resin (A) contains at least an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) copolymerizable with the (Aa) and / or a cyclic ether group- Ac) as a binder resin.

Examples of the binder resin (A) used in the photosensitive resin composition of the present invention include a binder resin (A1) and a binder resin (A2). The binder resin (A1) exhibits alkali solubility, and the binder resin (A2) exhibits alkali solubility and reactivity due to the action of at least one of light and heat.

As the binder resin (A1), at least one kind (Aa) (hereinafter, sometimes referred to as (Aa)) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, , And a monomer (Ab) (except for (Aa)) (hereinafter occasionally referred to as "Ab").

(A-a) include, for example, aliphatic unsaturated carboxylic acids and / or aliphatic unsaturated carboxylic anhydrides, 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 the above-mentioned 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- (meth) acryloyloxyethyl] Esters;

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

Of these, acrylic acid, methacrylic acid or maleic anhydride are preferably used in terms of copolymerization reactivity and alkali solubility. These are used alone or in combination.

(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 [ (Meth) acrylate], 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], dicyclo [ Cyclic alkyl esters of acrylic acid such as pentafluoroethyl acrylate, pentafluoroethyl 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;

2,2,1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [ 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-methoxybicyclo [2.2.1] hepto-2- 2,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] ) Bicyclo [2.2.1] hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept- Ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept- 2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- 2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [ 2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride (hydamic anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept- 2,6-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] 2.2.1] hept-2-ene, and 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

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-acrylydinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and alkali solubility.

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

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

In the copolymer obtained by copolymerizing (Aa) and (Ab), the proportion of constituent components derived from each other is in the range of the molar fraction when the total molar number of constituent components constituting the copolymer is 100 mol% .

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

(A-b); 60 mol% to 98 mol%

Further, it is more preferable that the ratio of the above components is in the following range.

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

(A-b); 65 mol% to 95 mol%

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

The binder resin (A1) can be prepared, for example, by the method described in the " Experimental Method of Polymer Synthesis " (published by Otsu Takayuki Co., Ltd., 1st Ed., 1st Ed., March 1, 1972) Can be prepared by reference to the literature.

Specifically, a predetermined amount of the units (Aa) and (Ab) constituting the copolymer, a polymerization initiator and a solvent are placed in a reaction vessel, and by replacing oxygen by nitrogen, stirring, heating, A polymer can be obtained. The resulting copolymer may be a solution after the reaction as it is, a solution which is concentrated or diluted, or a solid (powder) obtained by re-precipitation or the like may be used.

The weight average molecular weight of the binder 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) having alkali solubility is within the above range, the coating property tends to be good, the film is not easily reduced during development, and the dropout of the non- It tends to be favorable.

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

The content of the binder resin (A1) usable in the photosensitive resin composition of the present invention is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 10% by mass relative to the solid content in the photosensitive resin composition, 70% by mass. When the content of the binder resin (A1) is within the above range, solubility in a developing solution is sufficient and development residue is not easily generated 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 portion tends to be favorable.

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

The binder resin (A2-1) is a copolymer of (A-a), (A-b) and a monomer (A-c) having a cyclic ether group having 2 to 4 carbon atoms (hereinafter sometimes referred to as "(A-c)").

The binder resin (A2-2) is a copolymer obtained by reacting a part of carboxyl groups derived from (Aa) with a cyclic ether group having 2 to 4 carbon atoms derived from (Ac) in a copolymer of (Aa) It is united.

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

(A-c) means a polymerizable compound having at least one kind of group selected from the group consisting of cyclic ether groups having 2 to 4 carbon atoms (e.g., epoxy group, oxetanyl group and tetrahydrofuryl group). (Ac) has at least one kind of group selected from the group consisting of cyclic ether groups having 2 to 4 carbon atoms, is preferably a compound having an unsaturated bond, and is selected from the group consisting of groups having a cyclic ether structure having 2 to 4 carbon atoms , And more preferably a compound having an acryloyl group or a methacryloyl group.

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

The above-mentioned monomer having an epoxy group means 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, for example. 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 also having an unsaturated bond.

Examples of the compound having an aliphatic epoxy group among monomers having an epoxy group include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) , Glycidyl vinyl ether, and compounds represented by the following formulas described in JP-A-7-248625.

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

Examples of the compound represented by the above formula include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether, -Methyl-m-vinylbenzyl glycidyl ether,? -Methyl-p-vinylbenzyl glycidyl 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 monomers having an alicyclic epoxy group among monomers having an epoxy group include monomers having an aliphatic monocyclic epoxy group and monomers having an aliphatic polycyclic epoxy group.

The monomer having an aliphatic monocyclic epoxy group as described above refers to a polymerizable compound having an epoxy group on the ring of an 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 and has a structure in which a monocyclic alicyclic hydrocarbon ring is condensed with an oxirane ring, Or a compound having a methacryloyl group.

Examples of the aliphatic monocyclic compound include cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. 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 [e.g., Celloxide 2000; (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate [e.g., CYROMER-A400; Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (e.g., cyclomer-M100; (Manufactured by Daicel Chemical Industries, Ltd.).

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 epoxy group is preferably a compound having an epoxy group on the ring of an aliphatic polycyclic compound and having an unsaturated bond and has a structure in which a ring of a polycyclic alicyclic hydrocarbon is condensed with an oxirane ring, Or a compound having a methacryloyl group.

Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricyclododecane, bicyclododecane, tricyclo Dodecane, etc. 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 kind of compound selected from the group consisting of

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

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

Specific examples of R ₁ and R ₂ include a hydrogen atom; An alkyl group 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- And a hydroxyl group-containing alkyl group such as a butyl group. Among them, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

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 a methylene group, an oxyethylene group, an oxyethylene group, an oxyethylene group, an oxypropylene group, a thiomethylene group, a thioethylene group, a thiopropylene group, an aminomethylene group, an aminoethylene group and an aminopropylene group. Among them, a single bond, a methylene group, an ethylene group, an oxymethylene group and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

Examples of the at least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) include compounds represented by the following formula (I ') and compounds represented by formula (II' Is preferably at least one kind of compound selected from the group consisting of

Formula (I ') and formula (II') according to, R ₁ 'and R _2' is wherein each of R ₁ And R < ₂ >.

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

Specific examples of the compound represented by formula (II) include compounds represented by formulas (II-1) to (II-15) ), Formula (II-5), Formula (II-7), Formula (II-9) and Formula (II-11) ), 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 any ratio. The mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, more preferably from 20: 80 to 80:20.

The monomer having an oxetanyl group as described above refers to a polymerizable compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic oxetanyl group. The oxetanyl group-containing monomer is preferably a compound having at least one group selected from the group consisting of an aliphatic oxetanyl group and an alicyclic 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- 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, 3-methyl- 3-ethyl-3-acryloxyethyloxetane and the like.

These are used alone or in combination.

The monomer having a tetrahydrofuryl group as mentioned above refers to a polymerizable compound having at least one kind of group selected from the group consisting of aliphatic tetrahydrofuryl groups and alicyclic tetrahydrofuryl groups. The monomer having tetrahydrofuryl group is preferably a compound having at least one group selected from the group consisting of an aliphatic tetrahydrofuryl group and an alicyclic tetrahydrofuryl group and having an unsaturated bond.

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

These are used alone or in combination.

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

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

(A-b); 1 mol% to 65 mol%

(A-c); 2 mol% to 95 mol%

Further, it is more preferable that the ratio of the above components is in the following range.

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

(A-b): 1 mol% to 60 mol%

(A-c); 5 mol% to 80 mol%

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

The binder resin (A2-1) can be prepared, for example, by the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Ed., March 1, 1972) Can be produced by referring to the cited document.

Specifically, a predetermined amount of a compound which derives the units (Aa), (Ab) and (Ac) constituting the copolymer, a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by nitrogen, , Stirring, heating, and warming to obtain a polymer. The resulting copolymer may be a solution after the reaction as it is, a solution which is concentrated or diluted, or a solid (powder) obtained by re-precipitation or the like may be used.

In producing the binder resin (A2-2), first (A-a) and (A-b) are copolymerized to prepare a copolymer. It is preferable that the ratio of the constituent components derived from each other is in a molar ratio with respect to the total number of moles of constituent components constituting the above copolymer within the following range.

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

(A-b); 50 mol% to 95 mol%

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

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

(A-b); 55 mol% to 90 mol%

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) An oxetanyl group or a tetrahydrofuryl group derived from the above-mentioned compound.

(A-c) is from 5 mol% to 80 mol%, preferably from 10 mol% to 75 mol%, and more preferably from 15 mol% to 70 mol%, based on the molar amount of (A-a).

When the composition ratio is within the above range, balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be improved.

The binder resin (A2-2) can be produced through a two-step process. For example, the method described in the document " Experimental Method of Polymer Synthesis " (published by Otsu Takayuki Co., Ltd., 1st edition, 1st edition, published on Mar. 1, 1972), and the method described in Japanese Patent Application Laid-Open No. 2001-89533 Can be produced with reference to the method.

Specifically, the first step will be described first. A predetermined amount of a compound which derives the units (Aa) and (Ab)) constituting the copolymer (that is, the binder resin) obtained by copolymerizing the components (Aa) and (Ab), the polymerization initiator and the solvent are placed in a reaction vessel, By replacing oxygen by oxygen, the binder resin can be obtained by stirring, heating, and warming in the absence of oxygen. The obtained resin may be a solution obtained after the reaction as it is, a solution obtained by concentration or dilution, or a solid (powder) obtained by re-precipitation or the like may be used. The weight average molecular weight of the resin 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 is within the above 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 satisfactorily discharged at the time of development, which is preferable .

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the molecular weight distribution is within the above range, the coating property and developability tend to be excellent.

Next, the process of the second step will be described. Subsequently, the atmosphere in the flask was replaced with air from nitrogen, and the content of the component (Ac) in the range of 5 mol% to 80 mol%, the molar number of the carboxyl group and the epoxy group, the oxetanyl group or the tetrahydrofuryl group (Aa) to (Ac) based on the total amount of the monomers (Aa) to (Ac) as the reaction catalyst and 0.001 to 5% by mass of the tricydimethylaminomethylphenol based on the total amount of the monomers (Aa) (Ac) can be reacted by continuing the reaction at 60 ° C to 130 ° C for 1 to 10 hours by adding 0.001% to 5% based on the total amount of the resin to the flask. Further, in the same manner as the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

In the binder resin (A2-3), it is preferable that the proportion of the constituent components derived from each other is in the following range in terms of the molar ratio with respect to the total number of moles of the constituent components constituting the binder resin (A2-3).

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

(A-c); 5 mol% to 95 mol%

Further, it is more preferable that the ratio of the above components is in the following range.

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

(A-c); 10 mol% to 90 mol%

When the composition ratio is within the above range, there is a tendency that storage stability, developability, solvent resistance, heat resistance and mechanical strength are improved.

The binder resin (A2-3) can be produced, for example, by the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, First Edition, March 1, 1972) It can be produced with reference to the cited documents.

Specifically, a predetermined amount of a compound which derives the units (Aa) and (Ac) constituting the copolymer, a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by nitrogen, , And warmed to obtain a polymer. The obtained copolymer may be used as it is, or may be a concentrated or diluted solution, and it may be a solid (powder) extracted by re-precipitation or the like.

Examples of the at least one compound (B) selected from the group consisting of the carboxylic acid anhydride and the compound having at least two carboxyl groups contained in the photosensitive resin composition of the present invention include polycarboxylic acid anhydrides, .

As the polyvalent carboxylic acid anhydride, for example,

Examples of the anhydrides include citric acid anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornenedicarboxylic acid, Aliphatic dicarboxylic acid anhydrides;

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 benzophenonetetracarboxylic acid anhydride;

And ester bond-containing acid anhydrides such as ethylene glycol bistrimellitate and glycerin tristrimellitate.

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

As the carboxylic acid anhydride, an epoxy resin curing agent comprising a commercially available colorless acid anhydride can be suitably used. Concretely, it is possible to use an epoxy resin such as Adeka Hardener EH-700 (trade name, hereinafter the same), Asahi Denka Kogyo Co., Ltd., Ricaside HH, Riccide MH-700 Kinia YH-306, Epikinia DX-126 (manufactured by Yucca Shell Epoxy Co., Ltd.), and the like.

As the polyvalent carboxylic 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.

These polycarboxylic acid anhydrides and polycarboxylic acids may be used alone or in combination of two or more.

The content of the compound (B) in the photosensitive resin composition of the present invention is preferably from 0.1% by mass to 20% by mass, more preferably from 0.1% by mass to 20% by mass, based on the total amount of the binder resin (A) Is 1% by mass to 15% by mass, more preferably 2% by mass to 10% by mass, and even more preferably 2% by mass to 8% by mass. If the content of the compound (B) is less than 0.1% by mass, the resolution may be lowered. On the other hand, when the content of the compound (B) exceeds 20 mass%, there is a fear that the residual film ratio is lowered.

Examples of the photopolymerizable compound (C) contained in the photosensitive resin composition of the present invention include monovalent monomers, bifunctional monomers, and other multifunctional monomers having three or more functional groups.

Specific examples of monofunctional monomers include nonylphenylcarbitol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- (Meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propoxylated nonylphenol (meth) acrylate or N-vinylpyrrolidone.

Specific 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 Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, Acrylate, 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.

Specific examples of other multifunctional monomers having three or more functional groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) Propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (Meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, dipentaerythritol (Meth) acrylate and acid anhydride, a reaction product of threitol penta (meth) acrylate and an acid anhydride, tripentaerythritol hepta (meth) acrylate and acid anhydride caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified pentaerythritol tri , Caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone (Meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone- Caprolactone-modified tripentaerythritol hepta (meth) acrylate , A reaction product of caprolactone-modified tripentaerythritol octa (meth) acrylate, a reaction product of caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, a reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride, Caprolactone-modified tripentaerythritol hepta (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.

Particularly, a multifunctional monomer having two or more functional groups is preferably used. These photopolymerizable compounds (C) may be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 60% by mass relative to the total amount of the binder resin (A) and the photopolymerizable compound (C) Mass%. When the content of the photopolymerizable compound (C) is within the above-mentioned range, the strength, smoothness, reliability and mechanical strength of the coating film and pattern tend to be favorable.

The photopolymerization initiator (D) contained in the photosensitive resin composition of the present invention is a compound that initiates polymerization by the action of light or heat, and is a compound that initiates polymerization by the action of light or heat. Examples of the photopolymerization initiator include a nonimidazole compound, an acetophenone compound, a triazine compound, an acylphosphine oxide compound Or a oxime-based compound is preferable, and a non-imidazole-based compound is particularly preferable because it is excellent in 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 and JP-A-6-75373), 2,2'-bis -Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) , 4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid- , Imidazole compounds in which the phenyl group at the 5'-position is substituted by a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.), and preferably 2,2'-bis 2-chlorophenyl) -4,4 ' , 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- Phenyl} -2-methylpropan-1-one, 2-hydroxy-1- {4- [4- (2- Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino 1- (4-morpholinophenyl) butan-1-one, 2- (3- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- 2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorophenyl) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-bromobenzyl) , 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Butanone, 2- (2-methyl-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) 2-( 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-isoquinoline- Oligomers of 1- (4-morpholinophenyl) -butanone and 2-hydroxy-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- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Examples of the oxime compounds include 0-ethoxycarbonyl-? -Oxyimino-1-phenylpropan-1-one, a compound represented by formula (IV) and a compound represented by formula (V).

As far as the effect of the present invention is not impaired, a photopolymerization initiator or the like can be further used in combination. Examples of the photopolymerization initiator include benzoin-based compounds, benzophenone-based compounds, and thioxanthone-based compounds.

More specifically, the following compounds may be used, and these may be used alone or in combination of two or more.

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'- Butyl peroxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

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

In addition, examples of the photopolymerization initiator include 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate or titanocene compounds.

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 (5) to (10).

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

The light and / or thermal cationic polymerization initiator may also be composed of an onium cation and an anion derived from a Lewis acid.

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 (2-chloroethoxy) sulfonium, dimethyl (3-bromoproxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, Dimethyl [tris (trichloromethyl) methyl] sulfone, dimethyl (8-nitrooctyloxy) sulfonium, dimethyl (18- trifluoromethyloctadecaneoxy) 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 anion derived from the Lewis acid include hexafluorophosphate, hexafluoroacetate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Preferred examples of the anion derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate.

Specific examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p (p-octylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexafluorophosphate, Iodonium hexafluorophosphate, iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluorophosphate, (p- ) Iodonium hexafluorophosphate, methylnaphthyl iodonium hexafluorophosphate, ethylnaphthyl iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-toluene) Tris (p-tert-butylphenyl) sulfide, tris (p-tert-butylphenyl) sulfone, hexafluorophosphate, tris (P-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexa (Methoxy) sulfonium hexafluorophosphate, dimethyl (ethoxy) sulfonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium hexafluorophosphate, dimethyl Phosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium hexafluorophosphate Dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloroethoxy) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, Sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) Fluorophosphate, dimethyl [tris (trichloromethyl) methyl] sulfonium hexafluorophosphate;

Iodonium hexafluoroacetate, bis (p-tert-butylphenyl) iodonium hexafluoroacetate, bis (p-octylphenyl) iodonium (P-octadecyloxyphenyl) iodonium hexafluoroacetate, bis (p-octadecyloxyphenyl) iodonium hexafluoroacetate, bis (p-octyloxyphenyl) iodonium hexafluoroacetate, (P-tolyl) (i-isopropylphenyl) iodonium hexafluoroacetate, methylnaphthyl iodonium hexafluoro (p-isopropylphenyl) iodonium hexafluoroacetate, Tetra (p-tolyl) sulfonium hexafluoroacetate, tris (p-isopropylphenyl) sulfonium hexafluoroacetate, triphenylsulfonium hexafluoroacetate, Rosinate, tris (2,6-dimethyl Phenyl) sulfonium hexafluoroacetate, tris (p-tert-butylphenyl) sulfonium hexafluoroacetate, tris (p-cyanophenyl) sulfonium hexafluoroacetate, tris (p- chlorophenyl) (Methoxy) sulfonium hexafluoroacetate, dimethyl (ethoxy) sulfonium hexafluoroacetate, dimethyl (methoxy) sulfonium hexafluoroacetate, dimethyl (Butoxy) sulfonium hexafluoroacetate, dimethyl (octyloxy) sulfonium hexafluoroacetate, dimethyl (octadecanoxy) benzenesulfonate, Sulfonium hexafluoroacetate, dimethyl (isopropoxy) sulfonium hexafluoroacetate, dimethyl (tert-butoxy) sulfonium hexafluoroacetate, dimethyl (cyclopentyloxy) sulfonium hexafluoroacetate Dimethyl (2-chloroethoxy) sulfonium hexafluoroacetate, dimethyl (cyclopentyloxy) sulfonium hexafluoroacetate, dimethyl (fluoromethoxy) sulfonium hexafluoroacetate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroacetate, dimethyl (18-naphthoyloxy) sulfonium hexafluoroacetate, dimethyl (Trichloromethyl) methyl] sulfonium hexafluoroacetate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroacetate, dimethyl [tris (trichloromethyl) methyl] sulfonium hexafluoroacetate, Nate;

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) Dimethyl [tris (trichloromethyl) methyl] sulfonium hexafluoroantimonate, dimethyl [tris (trichloromethyl) methyl] sulfonium hexafluoroantimonate;

(Pentafluorophenyl) borate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, bis (Pentafluorophenyl) borate, bis (p-octylphenyl) borate, bis (p-octylphenyl) iodonium tetrakis ), Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis Iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyl iodonium tetrakis (pentafluorophenyl) borate, ethyl naphthyl iodonium tetra (p-tolyl) Kiss (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, dimethyl (Pentafluorophenyl) borate, dimethyl (isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (Cyclopentyloxy) 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 furnace (Pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl [tris (trichloromethyl) methyl] sulphonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxyisopropoxy) sulfonium tetrakis (P-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, ), Iodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p- tolyl) iodonium hexafluoroacetate, Tolyl) (p-isopropylphenyl) (P-tert-butylphenyl) iodonium hexafluoroacetate, triphenylsulfonium hexafluoroacetate, tris (pt-butylphenyl) sulfonium hexafluoroacetate, Iodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tolyl) Bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentafluorophenyl) borate , Tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borane (P-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, and the like are more preferable. triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, (Pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate.

The photopolymerization initiator (D) may be used in combination with the photopolymerization initiator (D-1) to such an extent as not to impair the effects of the present invention. Alternatively, the polymerization initiator may be used in a plurality of combinations.

Examples of the photopolymerization initiator (D-1) include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, compounds represented by formula (III), compounds represented by formula (A-1) .

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

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

The polyfunctional thiol compound is a compound having two or more thiol groups in the molecule. Among them, a compound having two or more aliphatic thiol groups is more preferable because the sensitivity of the photosensitive resin composition of the present invention becomes high.

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 tris thiopropionate, trimethylolpropane tris thioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl Pentaerythritol tetrakis (3-mercaptobutyrate) or 1,4-bis (3-mercaptobutyryloxy) butane, and the like.

The content of the polyfunctional thiol compound is preferably 0.1% by mass to 20% by mass, more preferably 1% by mass to 10% by mass relative to the total amount of the binder resin (A) and the photopolymerizable compound (C) to be. When the content of the polyfunctional thiol compound is within the above range, the sensitivity is high and the developing property tends to be good, which is preferable.

As the photopolymerization initiator (D-1), a compound represented by the following formula (III) may be used.

In the formula (III), the dotted line 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 a benzene ring and a naphthalene ring.

Examples of the aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom include benzene ring, methylbenzene ring, dimethylbenzene ring, ethylbenzene ring, propylbenzene ring, butylbenzene ring, pentylbenzene ring, hexylbenzene ring, cyclohexylbenzene ring Examples of the ring include a 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, .

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- Methyl-n-butyl group, a 1-methyl-n-butyl group, a 1-methyl- Dimethyl-n-propyl group, an n-hexyl group, and a cyclohexyl group.

Examples of the alkyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methyl- Butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2- N-propyl group, a 2-dimethyl-n-propyl group, a 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 naphthyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonapthyl group.

As the compound represented by the formula (III), 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-chlorobenzothiazolin,

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 [l, 2-d] thiazoline,

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

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

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

2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [l, 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 [l, 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 [l, 2-d] oxazoline, and the like.

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

As the photopolymerization initiator (D-1), at least one compound selected from the group consisting of the formulas (A-1) and (A-2) may be used.

In the formulas (A-1) and (A-2), 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 atom contained in the aromatic ring, the alkyl group or the aryl group may be substituted with an oxygen atom, a nitrogen atom, a sulfur atom or a halogen atom.

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

Examples of the aromatic rings 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, Examples of the ring include a 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, a phenanthrene ring, A benzo [a] pyrene ring, a benzo [e] pyrene ring, a perylene ring, and derivatives thereof.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1-methyl- Methyl-n-butyl group, a 1-methyl-n-butyl group, a 1-methyl- N-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2-chloro- .

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

Specific examples of the compound represented by formula (A-1) or (A-2) include

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

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

Dialkoxynaphthacene such as dimethoxynaphthalene, dimethoxynaphthacene, diethoxynaphthacene, dipropoxynaphthacene, diisopropoxynaphthacene, and dibutoxynaphthacene, but the present invention is not limited thereto.

The content of the photopolymerization initiator (D) is preferably 0.1% by mass to 40% by mass, more preferably 1% by mass to 30% by mass relative to the total amount of the binder resin (A) and the photopolymerizable compound (C) %to be.

The content of the photopolymerization initiator (D-1) is preferably 0.01% by mass to 50% by mass, and more preferably 0.1% by mass to 40% by mass on the same basis as described above.

The content of the compound represented by at least one species selected from the group consisting of the formulas (A-1) and (A-2) is preferably 50% to 100% , More preferably 60% to 100%, and still more preferably 65% to 100%. When the content of the compound represented by at least one kind selected from the group consisting of the formula (A-1) and the formula (A-2) is in the above range, when the coating film is formed using the photosensitive resin composition containing the compound, The transparency of the film becomes favorable.

When the total amount of the photopolymerization initiator (D) is within the above range, the photosensitive resin composition becomes highly sensitive, and the strength of the coating film or pattern formed by using the photosensitive resin composition described above and the surface smoothness Is preferable because it tends to be good. In addition, when the amount of the photopolymerization initiator (D-1) is in the above range, the sensitivity of the obtained photosensitive resin composition becomes higher, and the productivity of the pattern formed using the above photosensitive resin composition tends to be improved desirable.

The photosensitive resin composition of the present invention may contain a solvent (E), if necessary. Examples of the solvent (E) include various organic solvents used in the field of the photosensitive resin composition, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether Ethylene glycol monoalkyl ethers such as ethylene glycol monoalkyl 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 and butoxybutyl acetate;

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, , Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Propyl methoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, propyl methoxyacetate, methyl ethoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, methyl butoxyacetic acid, butoxyacetic acid, butoxyacetic acid Methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 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, propyl 3-butoxypropionate, 3-propoxypropionate, 3- Esters such as butyl butoxy propionate;

Cyclic ether radicals such as tetrahydrofuran and pyran;

and cyclic esters such as? -butyrolactone.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 占 폚 to 200 占 폚 in the above solvents are preferable from the viewpoint of coatability and drying property. Specific examples of the organic solvent having a boiling point of 100 ° C to 200 ° C include alkylene glycol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate, and 3-ethoxypropionate -Methoxypropionate, and the like, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl acetate, 3-ethoxypropionic acid Ethyl and methyl 3-methoxypropionate.

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

The content of the solvent (E) in the photosensitive resin composition of the present invention is preferably 60% by mass to 90% by mass, more preferably 65% by mass to 85% by mass, based on the mass of the photosensitive resin composition. When the content of the solvent (E) is in the above range, it is coated with a coating device such as a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater), an ink jet, a roll coater, It is preferable that the coating property is improved.

The photosensitive resin composition of the present invention contains substantially no coloring agent such as a pigment and a dye. That is, in the photosensitive resin composition of the present invention, the content of the colorant in the total composition is, for example, less than 10% by mass, preferably less than 1% by mass.

(F) such as a filler, another polymer compound, a leveling agent, 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 .

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

Specific examples of the other polymer compound include thermosetting resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane .

As the leveling agent, a commercially available surfactant can be used, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric surfactants. They may be used in combination. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, polyethyleneimine (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink Chemical Industry Co., (Manufactured by EFKA CHEMICALS), Sulfur (manufactured by ZEONEKA CO., LTD.), EFKA (manufactured by EFKA CHEMICALS CO., LTD.), Fluororads (manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surfron , PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

As the adhesion promoter, silane compounds are preferable, and specific examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) Aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- 3-mercaptopropyltrimethoxysilane, and the like.

Specific 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 -butyl-4-hydroxy- ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- Methylphenyl) propionyloxy-1,1-dimethylethyl] - 2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6- 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-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butylphenyl) (3H, 5H) -triene, 3,3 ', 3 ", 5,5', 5 ' - (mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5- tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and the like.

Specific examples of the ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3- [3- tert- Phenyl] propionate, 2- [4 - [(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6 (2-hydroxy-3- (2'-ethyl) hexyl) oxy] -2-hydroxyphenyl (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- Butylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol- 2- (3-tert-butyl-2-hydroxy-5-methyl- -Methylphenyl) -5-chlorobenzotriazole or alkoxybenzophenone, and the like.

Specific 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- Diamine, decanedioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl (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 material 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.

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

The method of applying the photosensitive resin composition of the present invention to the surface of the base material is not particularly limited, and examples thereof include a spin coater, a slit & spin coater, a slit coater (sometimes referred to as a die coater or a curtain flow coater) , A dip coater, or the like.

The photosensitive resin composition of the present invention can be obtained by coating a coating film having a thickness of 3 占 퐉 after heat curing (e.g., 100 占 폚 to 250 占 폚 for 5 minutes to 3 hours) using a spectrophotometer under the condition of a measurement wavelength of 400 nm to 700 nm When the transmittance is measured, the transmittance is 90% or more, preferably 95% or more. This makes it possible to provide a coating film excellent in transparency.

The photosensitive resin composition of the present invention can be applied, for example, on a glass substrate, a film substrate, a substrate on which a color filter or a driving circuit is formed, and subjected to photo-curing and development to form a coating film or a pattern.

First, this photosensitive resin composition is applied onto a substrate (usually glass) or a layer formed of a solid component of a previously formed photosensitive resin composition, and then pre-baked from the applied photosensitive resin composition layer to remove volatile components such as a solvent, A cured coating film is obtained. The thickness of the uncured coating film at this time is approximately 1 to 6 占 퐉. The ultraviolet rays generated from the mercury lamp or the light emitting diode are irradiated to the thus obtained uncured coating film through a mask for forming a desired pattern.

Further, in pattern formation, the line width can be appropriately controlled by the mask size.

In recent exposures, light having a wavelength of less than 350 nm is cut by using a filter cutting the wavelength region, or light having a wavelength of about 436 nm, around 408 nm, and around 365 nm, And selectively extracted by using a filter to uniformly irradiate the entire exposed portion with parallel rays. It is preferable to use a mask aligner, a stepper, or the like so that the mask and the substrate are accurately aligned at this time. After that, the coating film on which the light irradiation is completed is brought into contact with the aqueous alkaline solution to dissolve the unexposed portion and then developed, whereby a desired coating film or pattern can be obtained. The developing method may be any of a liquid method, a dipping method, and a spray method. The substrate may be further tilted at an arbitrary angle at the time of development.

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

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

Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogen phosphate, ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, potassium carbonate, Sodium carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, and ammonia.

Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, mono Isopropylamine, diisopropylamine, ethanolamine and the like. These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01% by mass to 10% by mass, and more preferably 0.03% by mass to 5% by mass.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, poly Oxyethylene sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific 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, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium naphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts.

These surfactants may be used alone or in combination of two or more.

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

After development, the substrate is washed with water, and post-baking may be further performed at 150 to 230 占 폚 for 10 to 180 minutes, if necessary.

By using the photosensitive resin composition of the present invention, a coating film or a pattern can be formed on the substrate or on the color filter substrate through each of the steps described above. This coating film or pattern is useful as a photo-spacer or a patternable overcoat used in a liquid crystal display device. When a photomask for hole formation is used for patterning exposure to an uncured coating film, a hole can be formed and is useful as an interlayer insulating film. Further, at the time of exposure to an uncured coating film, a transparent film can be formed only by front exposure, heat curing, or heat curing without using a photomask, and this transparent film is useful as an overcoat and can also be used for a touch panel.

By embedding a coating film or a pattern thus obtained in a display device such as a liquid crystal display device, a display device of excellent quality can be manufactured with a high yield.

According to the photosensitive resin composition of the present invention, it is possible to form a pattern with high transmittance exhibiting a sufficient resolution.

[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 examples,% and parts representing the content or amount are on a mass basis 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 obtain a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass 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, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate [compound represented by formula (I-1) and compound represented by formula (II-1) : 50 parts by mass], and 140 parts by mass of 3-methoxybutyl acetate to prepare a solution. The solution was added dropwise to a flask heated at 70 ° C for 4 hours using a dropping funnel Respectively. On the other hand, a solution prepared by dissolving 30 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in 225 parts by weight of 3-methoxybutyl acetate was dropped into a flask over 4 hours using a separate dropping funnel Respectively. (Resin Aa) having a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content) was maintained at 70 캜 for 4 hours after the dropwise addition of the polymerization initiator solution was completed. ≪ / RTI > The obtained resin Aa had a weight average molecular weight (Mw) of 1.3 x 10 ⁴ and a molecular weight distribution (Mw / Mn) of 2.50.

(Measurement of molecular weight)

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of Resin Aa was carried out by the GPC method under the following conditions.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

The ratio of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution (Mw / Mn).

[Example 1]

(50 parts in terms of solid content), 3 parts of fumaric anhydride (B), 50 parts of dipentaerythritol hexaacrylate (C), 2 parts of 2,2'- 4 parts of bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (D) and 0.5 parts of 2- (2-naphthoylmethylene) -3-methylbenzothiazoline , 3 parts of pentaerythritol tetrakisthiopropionate (D), 0.8 parts of IRGANOX 3141 (manufactured by Ciba Specialty Chemicals) (F), 58 parts of propylene glycol monomethyl ether acetate, 42 parts of 3-ethoxyethyl propionate, 7 parts of methoxy-1-butanol and 9 parts of 3-methoxybutyl acetate were mixed to obtain a photosensitive resin composition (1).

≪ Average transmittance of the composition >

The average transmittance (%) at 400 nm to 700 nm was measured with respect to the photosensitive resin composition (1) using an ultraviolet visible spectrophotometer (V-650DS; manufactured by Nippon Gijutsu KK) (quartz cell, optical path length: ) Were measured.

≪ Average transmittance of the film &

Using the photosensitive resin composition (1), a cured film was produced under the following conditions so that the film thickness after curing became 3 占 퐉.

A 2 inch square glass substrate (# 1737; made by Corning) was washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin composition (1) was exposed on this glass substrate at an exposure dose (405 nm) of 200 mJ / cm ² and spin-coated to a film thickness after development, washing and post-baking to 3.0 μm, Lt; RTI ID = 0.0 > 90 C < / RTI > for 3 minutes.

An average transmittance (%) at 400 nm to 700 nm was measured for a cured film obtained by using a microscopic spectroscopic photometry apparatus (OSP-SP200; manufactured by OLYMPUS CO., LTD.).

The higher the transmittance means the smaller the absorption.

[Production of pattern 1]

A glass substrate (# 1737; made by Corning) having a 2-inch square was sequentially washed with a neutral detergent, water and alcohol, and then dried. The photosensitive resin composition (1) was exposed on this glass substrate at an exposure amount (405 nm) of 200 mJ / cm ² , spin-coated so as to have a film thickness after development, washing and post-baking to 3.0 탆, Lt; 0 > C for 3 minutes. After cooling, the distance between the substrate coated with this photosensitive resin composition (1) and the quartz glass photomask was set to 10 μm, exposure was performed with an exposure machine (TME-150 RSK; Manufactured by Topcon Co., Ltd., a light source; Ultra-high pressure mercury lamp] at an exposure amount of 100 mJ / cm ² (405 nm standard) in an air atmosphere. The irradiation with the photosensitive resin composition (1) at this time was carried out using an optical filter (LU0400; (Manufactured by Asahi Spectroscopy), and light of 400 nm or less was cut and used. Further, as a photomask, a photomask having a pattern (having a square translucent portion with a side length of 20 탆 and an interval of 100 탆 between these squares) was formed on the same plane was used.

After light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 DEG C for 100 seconds and developed. After washing with water, the coated film was post-baked at 220 DEG C for 20 minutes in an oven, 1.

<Line width>

The obtained pattern was measured by a three-dimensional non-contact surface shape measurement system (Micromap MM527N-PS-M100: manufactured by Ryoka System Co., Ltd.). With respect to the pattern height, the line width was 5% from the substrate surface.

The smaller the line width is, the better the resolution is.

[Example 2]

A photosensitive resin composition was obtained so as to have the composition shown in Table 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]

A photosensitive resin composition was obtained so as to have the composition shown in Table 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]

A photosensitive resin composition was obtained so as to have the composition shown in Table 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Table 1]

From the results of Examples 1 to 3 shown in Table 1, it can be seen that a pattern showing excellent resolution can be formed by using a specific compound. On the other hand, in Comparative Example 1, a pattern having sufficient resolution could not be obtained.

Since the photosensitive resin composition of the present invention can form a pattern with a high transmittance showing excellent resolution, it is possible to use a coating layer such as an overcoat, a photo spacer, an insulating film, a projection for controlling liquid crystal orientation, It can be suitably used for forming a coating film or a pattern to be used.

Claims (13)

At least one compound (B) selected from the group consisting of a binder resin (A), a carboxylic acid anhydride and a compound having at least two carboxyl groups, a photopolymerizable compound (C), and a photopolymerization initiator (D) Wherein the binder resin (A) comprises at least one kind of monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa), a monomer (Ab) copolymerizable with the above (Aa) And a monomer (Ac) having a cyclic ether group, and does not contain a coloring agent. The positive resist composition according to claim 1, wherein the binder resin (A) is at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa) and a monomer having a cyclic ether group having 2 to 4 carbon atoms ) As a binder resin. The photosensitive resin composition according to claim 1 or 2, wherein the monomer (A-c) having a cyclic ether group having 2 to 4 carbon atoms is a monomer having an epoxy group. The photosensitive resin composition according to claim 3, wherein the monomer having an epoxy group is a monomer having an aliphatic polycyclic epoxy group. The photosensitive resin composition according to claim 4, wherein the monomer having an aliphatic polycyclic epoxy group is at least one compound selected from the group consisting of a compound represented by formula (I) and a compound represented by formula (II).

[In the formulas (I) and (II), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ₁ And X ₂ each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may contain a hetero atom. The positive photosensitive composition as claimed in claim 1 or 2, wherein at least one monomer selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Aa) is an aliphatic unsaturated carboxylic acid, an aliphatic unsaturated carboxylic acid anhydride, An aliphatic unsaturated carboxylic acid and an aliphatic unsaturated carboxylic acid anhydride. The positive resist composition according to claim 5, wherein at least one compound selected from the group consisting of the compound represented by formula (I) and the compound represented by formula (II) is a compound represented by formula (1 ') and a compound represented by formula Wherein the photosensitive resin composition is at least one compound selected from the group consisting of compounds.

[In the formulas (I ') and (II'), R ₁ 'and R ₂ ' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.] 3. The photosensitive resin composition according to claim 1 or 2, wherein at least one compound (B) selected from the group consisting of a carboxylic anhydride and a compound having at least two carboxyl groups is a carboxylic acid anhydride. delete A pattern formed using the photosensitive resin composition according to claim 1 or 2. A display device comprising the pattern according to claim 10. A coating film formed using the photosensitive resin composition according to claim 1 or 2. A display device comprising the coating film according to claim 12.