JP2014052401A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition from which a pattern can be formed at a low temperature.SOLUTION: The photosensitive resin composition comprises a binder resin (A), a polymerizable compound (B) expressed by formula (I), and a photopolymerization initiator (C). In the formula, Rrepresents a hydrogen atom or a methyl group; and X represents -R-O-R-, where Rrepresents a single bond or an alkylene group having 1 to 5 carbon atoms and Rrepresents an alkylene group having 1 to 3 carbon atoms and having a hydroxyl group. The binder resin (A) contains one of a vinyl toluene skeleton, a tricyclodecane skeleton and dicyclopentadiene skeleton. The photosensitive resin composition further contains a colorant (D). A pattern formed of the above photosensitive resin composition and a display device including the pattern are also disclosed.

Description

  The present invention relates to a photosensitive resin composition.

  A color filter used in a display device such as a liquid crystal display panel, an electroluminescence panel, a plasma display panel, or electronic paper is manufactured using a photosensitive resin composition. As such a photosensitive resin composition, a photosensitive resin composition containing dipentaerythritol hexaacrylate as a polymerizable compound is known (Patent Document 1).

Japanese Patent Laying-Open No. 2005-157311

  When a pattern is formed on a substrate having low heat resistance such as a plastic substrate and used for applications such as a color filter, the pattern having a solvent resistance required for the application is low enough not to deform the substrate. It is necessary to form at a temperature, and development of a photosensitive resin composition capable of forming a pattern at such a temperature has been demanded.

（Ｒ_１は水素原子またはメチル基を表し、ＸはＸは−Ｒ_２−Ｏ−Ｒ_３−を表し、Ｒ_２は単結合又は炭素数１〜５のアルキレン基を表し、Ｒ_３は水酸基を有する炭素数１〜３のアルキレン基を表す）
[２] 重合開始剤（Ｃ）が、下記式（ＩＩ）で示される構造を有する重合開始剤である[１]記載の感光性樹脂組成物。

（式中、＊はそれぞれ結合手を表す。）
[３] （Ｉ）で示される重合性化合物が下記式（ＩＩＩ）で表される化合物である[１]または[２]記載の感光性樹脂組成物。

[４] バインダー樹脂（Ａ）がビニルトルエン骨格、トリシクロデカン骨格、ジシクロペンタジエン骨格のいずれかを含有する[１]〜[３]のいずれかに記載の感光性樹脂組成物。
[５] さらに、着色剤（Ｄ）を含む[１]〜[４]のいずれかに記載の感光性樹脂組成物。
[６] [１]〜[５]のいずれかに記載の感光性樹脂組成物により形成されるパターン。
[７] [６]記載のパターンを含む表示装置。 The present invention provides the following [1] to [7].
[1] A photosensitive resin composition comprising a binder resin (A), a polymerizable compound (B) represented by the following formula (I), and a polymerization initiator (C).
<Formula (I)>

(R ₁ represents a hydrogen atom or a methyl group, X represents —R ₂ —O—R ₃ —, R ₂ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₃ represents a hydroxyl group. Represents an alkylene group having 1 to 3 carbon atoms)
[2] The photosensitive resin composition according to [1], wherein the polymerization initiator (C) is a polymerization initiator having a structure represented by the following formula (II).

(In the formula, each * represents a bond.)
[3] The photosensitive resin composition according to [1] or [2], wherein the polymerizable compound represented by (I) is a compound represented by the following formula (III).

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the binder resin (A) contains any one of a vinyltoluene skeleton, a tricyclodecane skeleton, and a dicyclopentadiene skeleton.
[5] The photosensitive resin composition according to any one of [1] to [4], further comprising a colorant (D).
[6] A pattern formed from the photosensitive resin composition according to any one of [1] to [5].
[7] A display device including the pattern according to [6].

  According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern at a low temperature.

（Ｒ_１は水素原子またはメチル基を表し、ＸはＸは−Ｒ_２−Ｏ−Ｒ_３−を表し、Ｒ_２は単結合又は炭素数１〜５のアルキレン基を表し、Ｒ_３は水酸基を有する炭素数１〜３のアルキレン基を表す） The photosensitive resin composition of the present invention contains a binder resin (A), a polymerizable compound (B) represented by the following formula (I), and a polymerization initiator (C).
<Formula (I)>

(R ₁ represents a hydrogen atom or a methyl group, X represents —R ₂ —O—R ₃ —, R ₂ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₃ represents a hydroxyl group. Represents an alkylene group having 1 to 3 carbon atoms)

  It is preferable that binder resin (A) used for the photosensitive resin composition of this invention is resin which shows alkali solubility. Here, alkali solubility refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound.

As the resin showing alkali solubility,
Resin (A-1): At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as “(a)”) and cyclic having 2 to 4 carbon atoms A copolymer obtained by polymerizing a compound (b) having ether (hereinafter sometimes referred to as “(b)”);
Resin (A-2): Monomer (c) copolymerizable with (a) and (b) (however, no cyclic ether having 2 to 4 carbon atoms is included) (hereinafter referred to as “(c)”) A copolymer obtained by polymerizing (a) and (b),
Resin (A-3): a copolymer obtained by polymerizing (a) and (c),
Resin (A-4): a resin obtained by reacting (b) with a copolymer obtained by polymerizing (a) and (c),
Resin (A-5): a resin obtained by reacting (a) with a copolymer obtained by polymerizing (b) and (c), and the like.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of copolymerization reactivity and alkali solubility.

  (B) refers to a polymerizable compound having a cyclic ether having 2 to 4 carbon atoms, such as at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring). (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and is a single monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group. A monomer is more preferable.

  Examples of (b) include a monomer (b1) having an oxiranyl group (hereinafter sometimes referred to as “(b1)”), a monomer (b2) having an oxetanyl group (hereinafter referred to as “(b2)”) And a monomer (b3) having a tetrahydrofuryl group (hereinafter sometimes referred to as “(b3)”).

The monomer (b1) having an oxiranyl group refers to a polymerizable compound having an oxiranyl group. Examples of (b1) include a monomer (b1-1) having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1-1)”), cycloalkene And a monomer (b1-2) having an epoxidized structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1-2)”).
(B1) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond, more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group, and (meth) acryloyloxy. (B1-2) having a group is more preferable.

  Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4, Examples thereof include 6-tris (glycidyloxymethyl) styrene and compounds described in JP-A-7-248625.

［式（ＩＶ）及び式（Ｖ）において、Ｒ^４及びＲ^５は、互いに独立に、水素原子または炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子はヒドロキシ基で置換されていてもよい。
Ｘ^１及びＸ^２は、互いに独立に、単結合、−Ｒ^６−、＊−Ｒ^６−Ｏ−、＊−Ｒ^６−Ｓ−または＊−Ｒ^６−ＮＨ−を表す。
Ｒ^６は、炭素数１〜６のアルカンジイル基を表す。
＊は、Ｏとの結合手を表す。］ Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Corporation), represented by the formula (IV) (Hereinafter sometimes referred to as “compound (IV)”), a compound represented by formula (V) (hereinafter sometimes referred to as “compound (V)”), and the like.

[In Formula (IV) and Formula (V), R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ¹ and ^{X 2} are each independently a single ^{bond, -R 6 -, * - R} 6 -O -, * - R 6 -S- or ^* -R represents a 6 -NH-.
R ⁶ represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1- Examples thereof include a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ⁴ and R ⁵ are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, a * —CH ₂ —O— group, a * —CH ₂ CH ₂ —O— group, and more preferably a single bond, * — CH ₂ CH ₂ -O- group. * Represents a bond with O.

Examples of compound (IV) include compounds represented by formula (IV-1) to formula (IV-15). Preferably Formula (IV-1), Formula (IV-3), Formula (IV-5), Formula (IV-7), Formula (IV-9), Formula (IV-11) to Formula (IV-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (IV-1), formula (IV-7), formula (IV-9), and formula (IV-15) can be mentioned.

Examples of the compound (V) include compounds represented by formula (V-1) to formula (V-15). Preferably Formula (V-1), Formula (V-3), Formula (V-5), Formula (V-7), Formula (V-9), Formula (V-11) to Formula (V-15) The compound represented by either of these is mentioned. More preferably, a compound represented by any one of formula (V-1), formula (V-7), formula (V-9), and formula (V-15) is used.

  Compound (IV) and Compound (V) can be used alone. They can also be mixed in any ratio. In the case of mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in compound (IV): compound (V). ~ 80: 20.

  The monomer (b2) having an oxetanyl group refers to a polymerizable compound having an oxetanyl group. (B2) is preferably a monomer having an oxetanyl group and an ethylenically unsaturated bond, and more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, Examples include 3-ethyl-3- (meth) acryloyloxyethyl oxetane.

The monomer (b3) having a tetrahydrofuryl group refers to a polymerizable compound having a tetrahydrofuryl group. (B3) is preferably a monomer having a tetrahydrofuryl group and an ethylenically unsaturated double bond, and more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.
Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of (c) include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and tert-butyl (meth) acrylate. Alkyl esters;
Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, dicyclopenta Nyl (meth) acrylate), (meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

Aryl (meth) acrylates or aralkyl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

  Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and alkali solubility.

In resin (A-1), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of the structural unit constituting the resin (A-1).
Structural unit derived from (a); 5-60 mol%, more preferably 10-50 mol%.
Structural unit derived from (b); 40 to 95 mol%, more preferably 50 to 90 mol%.
When the ratio of the structural unit of the resin (A-1) is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
As the resin (A-1), a resin in which (b) is (b1) is preferable, and a resin in which (b) is (b1-2) is more preferable.

  Resin (A-1) is, for example, a method described in the document “Experimental Method of Polymer Synthesis” (Takayuki Otsu, published by Chemical Dojin Co., Ltd. It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a method in which a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and oxygen is substituted with nitrogen, thereby deoxidizing, stirring, heating, and keeping warm. Is exemplified. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as a solvent for the colored photosensitive composition.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the same solvent as the solvent (E) described later as the solvent during the polymerization, the solution after the reaction can be used as it is, and the production process can be simplified.

In resin (A-2), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all structural units constituting the resin (A-2).
Structural unit derived from (a); 2 to 40 mol%, more preferably 5 to 35 mol%.
Structural unit derived from (b); 2-95 mol%, more preferably 5-80 mol%.
Structural unit derived from (c); 1 to 65 mol%, more preferably 1 to 60 mol%.
When the ratio of the structural unit of the resin (A-2) is in the above range, storage stability, developability, solvent resistance, heat resistance and mechanical strength tend to be good.
As the resin (A-2), a resin in which (b) is (b1) is preferable, and a resin in which (b) is (b1-2) is more preferable.
Resin (A-2) can be manufactured by the same method as resin (A-1).

In resin (A-3), it is preferable that the ratio of the structural unit derived from each monomer exists in the following ranges with respect to the total number of moles of all structural units constituting the resin (A-3).
Structural unit derived from (a); 2 to 40 mol%, more preferably 5 to 35 mol%.
Structural unit derived from (c); 60-98 mol%, more preferably 65-95 mol%.
When the ratio of the structural unit of the resin (A-3) is in the above range, the storage stability, developability, and solvent resistance tend to be good.
Resin (A-3) can be manufactured by the same method as resin (A-1).

  Resin (A-4) and resin (A-5) can be manufactured through a two-step process, for example. In this case as well, the method described in the above-mentioned document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Printing, published on March 1, 1972), It can be produced with reference to the method described in JP 89533.

First, the resin (A-4) is obtained as a first step in the same manner as in the method for producing the resin (A-1) described above to obtain a copolymer of (a) and (c).
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder.
The ratio of the structural units derived from (a) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (a); 5 to 50 mol%, more preferably 10 to 45 mol%.
Structural unit derived from (c); 50 to 95 mol%, more preferably 55 to 90 mol%.

Next, as a second step, the carboxylic acid (a) and a part of the carboxylic anhydride derived from the obtained copolymer are reacted with the cyclic ether (b). Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.
Specifically, following the above, the atmosphere in the flask was replaced from nitrogen to air, and 5 to 80 mol% (b) of a reaction catalyst of a carboxy group and a cyclic ether with respect to the number of moles of (a) ( For example, tris (dimethylaminomethyl) phenol) is 0.001 to 5% by mass with respect to the total amount of (a), (b) and (c), and a polymerization inhibitor (such as hydroquinone) is (a), 0.001-5 mass% is put in a flask with respect to the total amount of (b) and (c), for example, it is made to react at 60-130 degreeC for 1 to 10 hours, and resin (A-4) is obtained. be able to. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
In this case, the number of moles of (b) is preferably 10 to 75 mole%, more preferably 15 to 70 mole%, with respect to the number of moles of (a). By setting the number of moles of (b) within this range, the balance between storage stability, solvent resistance and heat resistance tends to be good.

  Specific examples of the resin (A-4) include a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate with glycidyl (meth) acrylate, (meth) acrylic acid / benzyl ( Resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylate, resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid / cyclohexyl (meth) acrylate, (meth) acrylic Resin obtained by reacting acid / styrene copolymer with glycidyl (meth) acrylate, resin obtained by reacting (meth) acrylic acid / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) Glycidyl (meth) acrylate was reacted with an acrylic acid / N-cyclohexylmaleimide copolymer. Fat, resin made by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / dicyclopentanyl (meta ) Resin prepared by reacting acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and (meth) acrylic acid / dicyclopentanyl (meth) acrylate / styrene copolymer glycidyl (meth) acrylate , A resin obtained by reacting (meth) acrylic acid / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / di Cyclopentanyl (meth) acrylate / N-cyclohexylmaleimi Copolymer glycidyl (meth) resins obtained by reacting an acrylate, glycidyl on copolymers of crotonic acid / dicyclopentanyl (meth) acrylate (meth) resins obtained by reacting acrylate;

  Crotonic acid / benzyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / cyclohexyl (meth) acrylate copolymer reacted with glycidyl (meth) acrylate, crotonic acid / Styrene copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / Methyl crotonic acid copolymer reacted with glycidyl (meth) acrylate, Crotonic acid / N-cyclohexylmaleimide copolymer Resin obtained by reacting glycidyl (meth) acrylate with the polymer, resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate, crotonic acid / di Cyclopentanyl (meth) acrylate / A resin obtained by reacting a copolymer of chlorhexyl (meth) acrylate with glycidyl (meth) acrylate, a resin obtained by reacting a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene with glycidyl (meth) acrylate, Resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonate copolymer with glycidyl (meth) acrylate, co-polymerization of crotonic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide Resin obtained by reacting glycidyl (meth) acrylate with the coalescence;

  A resin obtained by reacting a maleic acid / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, and a resin obtained by reacting a maleic acid / benzyl (meth) acrylate copolymer with glycidyl (meth) acrylate , A resin obtained by reacting maleic acid / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, a resin obtained by reacting maleic acid / styrene copolymer with glycidyl (meth) acrylate, maleic acid / maleic acid Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of methyl, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of maleic acid / N-cyclohexylmaleimide, maleic acid / dicyclopentanyl (meth) Of acrylate / benzyl (meth) acrylate Resin obtained by reacting glycidyl (meth) acrylate with a polymer, resin obtained by reacting maleic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer with glycidyl (meth) acrylate, maleic acid / Resin obtained by reacting dicyclopentanyl (meth) acrylate / styrene copolymer with glycidyl (meth) acrylate, maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate copolymer with glycidyl (meth) Resin in which acrylate is reacted, Resin in which glycidyl (meth) acrylate is reacted with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide;

  Resin obtained by reacting (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate copolymer with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / benzyl (meth) Resin obtained by reacting glycidyl (meth) acrylate with a copolymer of acrylate, resin obtained by reacting glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate, A resin obtained by reacting glycidyl (meth) acrylate with a copolymer of meth) acrylic acid / maleic anhydride / styrene, and glycidyl as a copolymer of (meth) acrylic acid / maleic anhydride / methyl (meth) acrylate Resin reacted with (meth) acrylate, (meth) acrylic acid / maleic anhydride / N-Si Resin obtained by reacting copolymer of rohexylmaleimide with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer glycidyl Resin in which (meth) acrylate is reacted, Resin in which glycidyl (meth) acrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate , (Meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / styrene resin reacted with glycidyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / di Cyclopentanyl (meth) acrylate / (meth) acrylic acid methyl A resin obtained by reacting a copolymer of glycidyl (meth) acrylate with a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide. Resin reacted with;

  A resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of (meth) acrylic acid / benzyl (meth) acrylate 3 , 4-Epoxycyclohexylmethyl methacrylate resin, (Meth) acrylic acid / cyclohexyl (meth) acrylate copolymer, 3,4-epoxycyclohexylmethyl methacrylate reaction resin, (Meth) acrylic acid / styrene A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (3), a resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of (meth) acrylic acid / methyl (meth) acrylate, (Meth) acrylic acid / N-cyclohex A resin obtained by reacting a copolymer of rumaleimide with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxy A resin obtained by reacting cyclohexylmethyl methacrylate, a resin obtained by reacting a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (meta ) A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of acrylic acid / dicyclopentanyl (meth) acrylate / styrene, (meth) acrylic acid / dicyclopentanyl (meth) acrylate / (meta ) Methacrylic acid A resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of 3,4-epoxycyclohexylmethyl with a copolymer of (meth) acrylic acid / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide Resin reacted with methacrylate;

  Crotonic acid / dicyclopentanyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate; Crotonic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl Resin in which methacrylate is reacted, Resin in which crotonic acid / cyclohexyl (meth) acrylate copolymer is reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / styrene copolymer in 3,4-epoxycyclohexylmethyl Resin reacted with methacrylate, Crotonic acid / methyl crotonate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, Crotonic acid / N-cyclohexyl maleimide copolymer treated with 3,4-epoxycyclohexyl Resin obtained by reacting til methacrylate, resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / dicyclopenta A resin obtained by reacting a copolymer of nyl (meth) acrylate / cyclohexyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, a copolymer of crotonic acid / dicyclopentanyl (meth) acrylate / styrene, Resin obtained by reacting 4-epoxycyclohexylmethyl methacrylate, resin obtained by reacting crotonic acid / dicyclopentanyl (meth) acrylate / methyl crotonic acid copolymer with 3,4-epoxycyclohexylmethyl methacrylate, crotonic acid / diethyl Kuropentaniru (meth) acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;

  A resin prepared by reacting a maleic acid / dicyclopentanyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and a maleic acid / benzyl (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl A resin reacted with methacrylate, a resin reacted with 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / cyclohexyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl with a copolymer of maleic acid / styrene A resin reacted with methacrylate, a resin reacted with maleic acid / methyl maleate copolymer with 3,4-epoxycyclohexylmethyl methacrylate, and a copolymer of maleic acid / N-cyclohexylmaleimide with 3,4-epoxycyclohexyl Resin in which butyl methacrylate is reacted, resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with maleic acid / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate copolymer, maleic acid / dicyclopenta Nyl (meth) acrylate / cyclohexyl (meth) acrylate copolymer reacted with 3,4-epoxycyclohexylmethyl methacrylate, maleic acid / dicyclopentanyl (meth) acrylate / styrene copolymer Resin obtained by reacting 4-epoxycyclohexylmethyl methacrylate, resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer of maleic acid / dicyclopentanyl (meth) acrylate / methyl maleate, maleic acid / diethyl Kuropentaniru (meth) acrylate / N- cyclohexyl maleimide copolymer resin obtained by reacting 3,4-epoxycyclohexylmethyl methacrylate;

  Resin obtained by reacting a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / benzyl Resin obtained by reacting (meth) acrylate copolymer with 3,4-epoxycyclohexylmethyl methacrylate; (meth) acrylic acid / maleic anhydride / cyclohexyl (meth) acrylate copolymer with 3,4-epoxycyclohexyl Resin in which methyl methacrylate is reacted, Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of (meth) acrylic acid / maleic anhydride / styrene, (meth) acrylic acid / maleic anhydride / Copolymer of methyl (meth) acrylate with 3,4-epoxy Resin obtained by reacting cyclocyclohexylmethyl methacrylate, resin obtained by reacting (meth) acrylic acid / maleic anhydride / N-cyclohexylmaleimide copolymer with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / A resin obtained by reacting a copolymer of maleic anhydride / dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate with 3,4-epoxycyclohexylmethyl methacrylate, (meth) acrylic acid / maleic anhydride / di Resin in which 3,4-epoxycyclohexylmethyl methacrylate is reacted with a copolymer of cyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate, (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) Acrylate / Styrene A resin prepared by reacting 3,4-epoxycyclohexylmethyl methacrylate with a copolymer, and a copolymer of (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / methyl (meth) acrylate. 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate and (meth) acrylic acid / maleic anhydride / dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide copolymer The resin etc. which made this react are mentioned.

Resin (A-5) obtains a copolymer of (b) and (c) as the first step in the same manner as in the method for producing resin (A-1) described above.
In this case, in the same manner as described above, the obtained copolymer may be used as it is as the solution after the reaction, or may be a concentrated or diluted solution, or a solid ( You may use what was taken out as a powder.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%, more preferably 10-90 mol%.
Structural unit derived from (c); 5-95 mol%, more preferably 10-90 mol%.

Further, in the same manner as in the production method of the resin (A-4), the cyclic ether derived from (b) in the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid that (a) has. It can be obtained by reacting an anhydride. A carboxylic acid anhydride may be further reacted with a hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol% with respect to the number of moles of (b). Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b), and (b1-1) is more preferable.

  Specific examples of the resin (A-5) include a resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, benzyl (meth) acrylate / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, resin in which (meth) acrylic acid is reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, styrene / glycidyl ( Resin in which (meth) acrylic acid is reacted with a copolymer of (meth) acrylate, Resin in which (meth) acrylic acid is reacted with a copolymer of methyl (meth) acrylate / glycidyl (meth) acrylate, N-cyclohexyl (Meth) acrylic acid was reacted with a maleimide / glycidyl (meth) acrylate copolymer Fatty, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate copolymer reacted with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / cyclohexyl (meta ) Acrylate / glycidyl (meth) acrylate copolymer reacted with (meth) acrylic acid; dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer (meth) acrylic acid , A resin obtained by reacting (meth) acrylic acid with a copolymer of (dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / glycidyl (meth) acrylate), dicyclopentanyl (meth ) Acrylate / N-cyclohexylmaleimide / glycidyl (me ) A copolymer of acrylate (meth) resins obtained by reacting an acrylic acid;

  Resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, resin obtained by reacting crotonic acid with a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate , A resin obtained by reacting crotonic acid with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, a resin obtained by reacting crotonic acid with a copolymer of styrene / glycidyl (meth) acrylate, methyl crotonate / glycidyl Resin obtained by reacting crotonic acid with copolymer of (meth) acrylate, resin obtained by reacting crotonic acid with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / glycidyl ( A) Resin obtained by reacting crotonic acid with a copolymer of acrylate, Resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, di Resin obtained by reacting crotonic acid with a copolymer of cyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / glycidyl (meth) acrylate And a resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

  Resin in which maleic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, and resin in which maleic acid is reacted with a copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate , A resin obtained by reacting a cyclohexyl (meth) acrylate / glycidyl (meth) acrylate copolymer with maleic acid, a resin obtained by reacting a styrene / glycidyl (meth) acrylate copolymer with maleic acid, methyl maleate / glycidyl Resin in which maleic acid is reacted with copolymer of (meth) acrylate, resin in which maleic acid is reacted with copolymer of N-cyclohexylmaleimide / glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate / benzyl (Meth) acrylate / glycidyl ( A) a resin obtained by reacting maleic acid with a copolymer of acrylate, a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, Resin in which maleic acid is reacted with a copolymer of cyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, copolymer of dicyclopentanyl (meth) acrylate / methyl maleate / glycidyl (meth) acrylate And a resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate;

  Resin prepared by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / glycidyl (meth) acrylate, copolymer of benzyl (meth) acrylate / glycidyl (meth) acrylate Resin in which (meth) acrylic acid and maleic anhydride are reacted with, a resin in which (meth) acrylic acid and maleic anhydride are reacted with a copolymer of cyclohexyl (meth) acrylate / glycidyl (meth) acrylate, styrene / Glycidyl (meth) acrylate copolymer reacted with (meth) acrylic acid and maleic anhydride, (meth) acrylic acid / glycidyl (meth) acrylate copolymer with (meth) acrylic acid and Resin reacted with maleic anhydride, (N-cyclohexylmaleimide / g Resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of sidyl (meth) acrylate, copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / glycidyl (meth) acrylate (Meth) acrylic acid and maleic acid to a resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / glycidyl (meth) acrylate Resin obtained by reacting anhydride, resin obtained by reacting (meth) acrylic acid and maleic anhydride with a copolymer of dicyclopentanyl (meth) acrylate / styrene / glycidyl (meth) acrylate, dicyclopentanyl ( (Meth) acrylate / methyl (meth) acrylate / glycidyl (meth) ) Resin obtained by reacting acrylate copolymer with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / glycidyl (meth) acrylate copolymer (meth) A resin reacted with acrylic acid and maleic anhydride;

  Resin obtained by reacting (meth) acrylic acid with a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate Resin in which (meth) acrylic acid is reacted with the polymer, Resin in which (meth) acrylic acid is reacted with the copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, styrene / 3,4-epoxy A resin obtained by reacting (meth) acrylic acid with a copolymer of cyclohexylmethyl methacrylate, a resin obtained by reacting (meth) acrylic acid with a copolymer of methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, N-cyclohexylmaleimide / 3, -A resin obtained by reacting (meth) acrylic acid with a copolymer of epoxycyclohexylmethyl methacrylate, a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate ( Resins in which (meth) acrylic acid is reacted, resins in which (meth) acrylic acid is reacted with a copolymer of dicyclopentanyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, di A resin obtained by reacting a copolymer of cyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid, dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxy Resin in which (meth) acrylic acid is reacted with a copolymer of cyclohexylmethyl methacrylate, (meth) in a copolymer of dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate A resin reacted with acrylic acid;

  A resin obtained by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with crotonic acid, and a copolymer of benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with croton Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, crotonic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer, croton Resin reacted with acid, Resin obtained by reacting crotonic acid with copolymer of methyl crotonate / 3,4-epoxycyclohexylmethyl methacrylate, N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting crotonic acid with a polymer, resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopenta Resin obtained by reacting crotonic acid with a copolymer of nyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexyl Resin obtained by reacting crotonic acid with a copolymer of methyl methacrylate, resin obtained by reacting crotonic acid with a copolymer of dicyclopentanyl (meth) acrylate / methyl crotonic acid / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopenta Le (meth) acrylate / N- cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer resin obtained by reacting an crotonic acid;

  Dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with maleic acid, benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer Acid-reacted resin, cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer, maleic acid-reacted resin, styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer Resin reacted with acid, Methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with maleic acid, N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Resin obtained by reacting maleic acid with a polymer, resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopenta Resin in which maleic acid is reacted with a copolymer of nyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentanyl (meth) acrylate / styrene / 3,4-epoxycyclohexyl Resin obtained by reacting maleic acid with a copolymer of methyl methacrylate, resin obtained by reacting maleic acid with a copolymer of dicyclopentanyl (meth) acrylate / methyl maleate / 3,4-epoxycyclohexylmethyl methacrylate, dicyclopenta Le (meth) acrylate / N- cyclohexyl maleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer resin obtained by reacting maleic acid;

  Resin prepared by reacting a copolymer of dicyclopentanyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, benzyl (meth) acrylate / 3,4-epoxycyclohexyl Resin prepared by reacting (meth) acrylic acid and maleic anhydride with a copolymer of methyl methacrylate, (meth) acrylic acid and maleic acid with a copolymer of cyclohexyl (meth) acrylate / 3,4-epoxycyclohexyl methyl methacrylate Resin obtained by reacting anhydride, resin obtained by reacting styrene / 3,4-epoxycyclohexylmethyl methacrylate copolymer with (meth) acrylic acid and maleic anhydride, methyl (meth) acrylate / 3,4- Of epoxy cyclohexyl methyl methacrylate Resin obtained by reacting (meth) acrylic acid and maleic anhydride with polymer, and (meth) acrylic acid and maleic anhydride reacted with N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate copolymer Resin, dicyclopentanyl (meth) acrylate / benzyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer reacted with (meth) acrylic acid and maleic anhydride, dicyclopenta Resin obtained by reacting a copolymer of nyl (meth) acrylate / cyclohexyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, dicyclopentanyl (meth) acrylate / Styrene / 3,4-epoxy A resin obtained by reacting a copolymer of hexylmethyl methacrylate with (meth) acrylic acid and maleic anhydride, and a copolymer of dicyclopentanyl (meth) acrylate / methyl (meth) acrylate / 3,4-epoxycyclohexylmethyl methacrylate. Resin obtained by reacting polymer with (meth) acrylic acid and maleic anhydride, (meth) acrylic copolymer with dicyclopentanyl (meth) acrylate / N-cyclohexylmaleimide / 3,4-epoxycyclohexylmethyl methacrylate Examples thereof include a resin obtained by reacting an acid and maleic anhydride.

  The polystyrene-reduced weight average molecular weight of the binder resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the binder resin (A) is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the unexposed part is easily removed during development. There is a tendency.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the binder resin (A) is preferably 1.1 to 6.0, and more preferably 1.2 to 4.0. When the molecular weight distribution is in the above range, the developability tends to be excellent.

  The acid value of binder resin (A) becomes like this. Preferably it is 20-200 mg-KOH / g, More preferably, it is 50-180 mg-KOH / g, More preferably, it is 70-150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the binder resin (A), and can be determined by titration with an aqueous potassium hydroxide solution.

  The content of the binder resin (A) is preferably 5 to 95 mass with respect to the total amount of the polymerizable compound (B) represented by the binder resin (A) and (I) and the polymerizable compound (B2) described later. %, More preferably, it is 20-90 mass%, More preferably, it is 30-80 mass%. When the content of the resin (A) is in the above range, developability, adhesion, solvent resistance of the cured pattern, and mechanical properties tend to be improved.

  10-70 mass% is preferable with respect to solid content of the photosensitive resin composition, and, as for content of binder resin (A) in the photosensitive resin composition of this invention, 20-50 mass% is more preferable. Here, solid content in this specification means the total amount of the component remove | excluding the solvent from the photosensitive resin composition.

（Ｒ_１は水素原子またはメチル基を表し、ＸはＸは−Ｒ_２−Ｏ−Ｒ_３−を表し、Ｒ_２は単結合又は炭素数１〜５のアルキレン基を表し、Ｒ_３は水酸基を有する炭素数１〜３のアルキレン基を表す） Examples of the polymerizable compound (B) represented by (I) include compounds (I-1) to (I-36) shown in the following table.

(R ₁ represents a hydrogen atom or a methyl group, X represents —R ₂ —O—R ₃ —, R ₂ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₃ represents a hydroxyl group. Represents an alkylene group having 1 to 3 carbon atoms)

が挙げられ、デナコールアクリレートＤＡ−１１１（以上、ナガセケムテックス製）として市販されている。 A particularly preferred example is represented by the polymerizable compound I-14.

And is commercially available as Denacol acrylate DA-111 (manufactured by Nagase ChemteX).

  The photosensitive resin composition of the present invention may further contain a polymerizable compound other than the polymerizable compound (B) represented by (I) (hereinafter sometimes referred to as “polymerizable compound (B2)”). Good. Examples of the polymerizable compound (B2) include monofunctional monomers, bifunctional monomers, and trifunctional or higher polyfunctional monomers.

  Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone and the like.

  Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and bisphenol A. Examples thereof include bis (acryloyloxyethyl) ether and 3-methylpentanediol di (meth) acrylate.

  Specific examples of the trifunctional or higher polyfunctional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol. Examples include hexa (meth) acrylate, a reaction product of pentaerythritol tri (meth) acrylate and an acid anhydride, a reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, and the like. Of these, a trifunctional or higher polyfunctional monomer is preferably used. These polymerizable compounds may be used alone or in combination of two or more.

  The ratio of the amount used of the polymerizable compound (B) represented by (I) and the polymerizable compound (B2) (mass ratio, polymerizable compound (B) / polymerizable compound (B2) represented by (I)) is The range of 100/0 to 10/90 is preferable.

  The total content of the polymerizable compound (B) and the polymerizable compound (B2) represented by (I) is a mass fraction when the content of the binder resin (A) is 100% by mass, preferably 10 to 10%. It is 90 mass%, More preferably, it is 20-80 mass%, More preferably, it is 30-70 mass%. When the total content of the polymerizable compound (B) and the polymerizable compound (B2) represented by (I) is in the above range, curing is sufficiently performed, and the film thickness ratio before and after development is improved, and the pattern It is preferable because the undercut is difficult to enter and the adhesiveness tends to be good.

The photosensitive resin composition of the present invention further contains a polymerization initiator (C).
The polymerization initiator (C) is not particularly limited as long as it is a compound capable of generating an active radical and an acid by the action of light and initiating polymerization of the polymerizable compound (B) represented by (I). A known polymerization initiator can be used.
Examples of the polymerization initiator (C) include biimidazole compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds. Moreover, you may use the photocationic polymerization initiator (For example, what is comprised from the onium cation and the anion derived from a Lewis acid) described in Unexamined-Japanese-Patent No. 2008-181087. Of these, oxime compounds are preferably used in terms of sensitivity.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913) and the like, 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 alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2. -Benzylbutan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1- (4-isopropenylphenyl) propan-1-one oligomers and the like Examples thereof include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Commercial products such as Irgacure 369, 907 (above, manufactured by BASF Japan Ltd.) may also be used.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Sulfonyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and commercial products such as Irgacure 819 (manufactured by BASF Japan) may be used.

（式中、＊はそれぞれ結合手を表す。）
かかるオキシム化合物を用いることにより、感光性樹脂組成物は高感度となり、またこれを用いて形成する膜は解像度及び耐溶剤性に優れパターンが良好となる。 The oxime compound is a polymerization initiator having a structure represented by the following formula.

(In the formula, each * represents a bond.)
By using such an oxime compound, the photosensitive resin composition has high sensitivity, and a film formed using this composition has excellent resolution and solvent resistance and a good pattern.

Specific examples of such oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine and the like, Irgacure (registered trademark) OXE-01, OXE-02 (above, manufactured by BASF Japan Ltd.), N- Commercial products such as 1919 (manufactured by ADEKA) may be used. Among these, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (the following formula) is preferably used.

  Furthermore, as the polymerization initiator (C), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples thereof include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.

  The polymerization initiator (C) is preferably used in combination with the polymerization initiation assistant (C-1) (particularly amines). The polymerization initiation assistant (C-1) is a compound or sensitizer that is used in combination with a polymerization initiator and is used to promote polymerization of a polymerizable compound that has been polymerized by the polymerization initiator. .

  Examples of the polymerization initiation assistant (C-1) include amine compounds, thiazoline compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferably used, but commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the thiazoline compound include compounds represented by formula (VI-1) to formula (VI-3).

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  The content of the polymerization initiator (C) is preferably 0.00 with respect to 100 parts by mass of the total amount of the polymerizable compound (B) and the polymerizable compound (B2) represented by the binder resins (A) and (I). 1 to 80 parts by mass, more preferably 1 to 60 parts by mass. When the total amount of the polymerization initiator (C) is within this range, a pattern can be formed with high sensitivity, and the chemical resistance, mechanical strength, and surface smoothness of the pattern tend to be good.

  When using the polymerization initiation assistant (C-1), the amount used is 100 parts by mass of the total amount of the polymerizable compound (B) and the polymerizable compound (B2) represented by the binder resins (A) and (I). On the other hand, it is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass. Moreover, it is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol per mol of the polymerization initiator (C). When the amount of the polymerization initiation assistant (C-1) is within this range, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

  The photosensitive resin composition of the present invention preferably further contains a colorant (D). Examples of the colorant (D) include pigments and dyes, but it is preferable to include a pigment in terms of heat resistance and light resistance.

Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists).
Specific examples of the organic pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Among them, C.I. I. Pigment yellow 138, 139, 150, C.I. I. Pigment red 177, 242, 254, C.I. I. Pigment violet 23, C.I. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Green 7, 36, and 58 are preferably used. These pigments may be used alone or in admixture of two or more.

  The pigment is optionally treated with rosin, surface treatment using a pigment derivative or pigment dispersant introduced with an acidic group or basic group, graft treatment on the pigment surface with a polymer compound, etc., sulfuric acid atomization Atomization treatment by a method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment by ion exchange method of ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  Commercially available surfactants can be used as the pigment dispersant, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, non-ionic, amphoteric, polyester-based, polyamine-based, and acrylic-based. Surfactant etc. are mentioned. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark, manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Ajisper (registered trademark, Ajinomoto) Fine Techno Co., Ltd.), Disperbyk (registered trademark, manufactured by Big Chemie) and the like. These can be used alone or in combination of two or more.

  When a pigment dispersant is used, the amount used is preferably 100% by mass or less, more preferably 5 to 50% by mass, based on the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  It does not specifically limit as a coloring agent (D), A well-known dye can be used, For example, an oil-soluble dye, an acidic dye, etc. are mentioned.

  These dyes are appropriately selected in accordance with the solubility in a solvent and the light fading resistance and spectral spectrum when a color filter pattern is formed using a colored curable resin composition containing the dye.

  The content of the colorant (D) is preferably 5 to 60% by mass and more preferably 5 to 45% by mass with respect to the solid content of the photosensitive resin composition. When the content of the colorant (D) is in the above range, a desired spectrum and color density can be obtained.

  The photosensitive resin composition of the present invention may contain a solvent (E). A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and used. These solvents may be used alone or in combination of two or more.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and the like methyl anisole.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate,
Examples include diethylene glycol monobutyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

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

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

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  Among the above solvents, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferably used among organic solvents having a boiling point of 120 ° C. or higher and 120 ° C. or lower at 1 atm from the viewpoint of coating properties and drying properties.

  Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the photosensitive resin composition, More preferably, it is 70-90 mass%. In other words, the solid content of the photosensitive resin composition is preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When content of a solvent (E) exists in the said range, there exists a tendency for the flatness at the time of application | coating to become favorable.

  The photosensitive resin composition of the present invention may contain a surfactant. Examples of the surfactant include a silicone surfactant, a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like. By including the surfactant, the flatness during application tends to be good.

  Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan GK) Manufactured) and the like.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain. Specifically, Florinart (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183 (DIC) ), Ftop (registered trademark) EF301, EF303, EF351, EF351, EF352 (manufactured by Mitsubishi Materials Denkasei), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass) And E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned. Preferably, MegaFac (registered trademark) F475 is used.

  The surfactant is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, still more preferably, based on the photosensitive resin composition. It is 0.01 mass% or more and 0.05 mass% or less. By containing the surfactant in this range, the flatness of the coating film can be improved.

  The photosensitive resin composition of the present invention contains various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents and the like as necessary. May be included.

  The photosensitive resin composition of the present invention comprises a binder resin (B2), a polymerization initiation assistant (C-1), a colorant (D), a solvent (E) and other components as necessary. It is obtained by mixing the polymerizable compound (B) represented by A) and (I) with the polymerization initiator (C).

Moreover, when mixing a pigment as a coloring agent (D), it is preferable to prepare in the following procedures, for example.
First, the pigment is preliminarily mixed with the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. At this time, part or all of the pigment dispersant and the binder resin (A) may be blended as necessary. In the obtained pigment dispersion, the remainder of the binder resin (A), the polymerizable compound (B) represented by (I), the polymerizable compound (B2), the polymerization initiator (C), etc. are used as necessary. The photosensitive resin composition can be obtained by adding other components and, if necessary, additional solvent as necessary to a predetermined concentration.

  Examples of the method for applying the photosensitive resin composition of the present invention to a substrate include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Apply using a coating device such as a dip coater, roll coater, bar coater, spin coater, slit & spin coater, slit coater (sometimes called a die coater, curtain flow coater, or spinless coater) or inkjet. Also good. Especially, it is preferable to apply using a slit coater, a spin coater, a roll coater or the like.

Examples of the method for drying the film applied to the substrate include methods such as heat drying, natural drying, ventilation drying, and vacuum drying. A plurality of methods may be combined.
As drying temperature, 10-120 degreeC is preferable and 25-100 degreeC is more preferable. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
The vacuum drying is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., and is, for example, 0.1 to 20 μm, preferably 1 to 6 μm.

The coating film after drying is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel light rays uniformly or the mask and the substrate can be accurately aligned.

After exposure, the coating film is brought into contact with a developer to dissolve a predetermined portion, for example, an unexposed portion, and developed, whereby a pattern can be obtained. As the developer, an organic solvent can be used, but it is preferable to use an aqueous solution of an alkaline compound because the exposed portion of the coating film is hardly dissolved or swollen by the developer and a pattern having a good shape can be obtained. .
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, Inorganic alkaline compounds such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia; tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, mono Examples include organic alkaline compounds such as ethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Sodium hydrogen carbonate and tetramethylammonium hydroxide are preferred.
The density | concentration in the aqueous solution of these inorganic and organic alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%.

The aqueous solution of the alkaline compound may contain a surfactant.
Surfactants include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine;
Anionic surfactants such as sodium lauryl alcohol sulfate, sodium oleyl alcohol sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylnaphthalenesulfonate;
And cationic surfactants such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
The concentration of the surfactant in the aqueous solution of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and particularly preferably 0.1 to 5% by mass.

  By further baking the pattern obtained as described above, a cured pattern can be obtained. The baking temperature is usually 25 ° C. or higher and 230 ° C. or lower, preferably 25 ° C. or higher and 200 ° C. or lower. The baking time is usually 1 to 300 minutes, preferably 1 to 180 minutes, more preferably 1 to 60 minutes.

  The pattern thus obtained is useful as, for example, a photospacer used in a liquid crystal display device, a patternable overcoat, and a color filter. In addition, the photosensitive resin composition of the present invention can be suitably used for forming a coating film or a pattern to be a pixel of a liquid crystal display device or an image sensor. Used as a part of a color filter, an array substrate, and a display device including the color filter and / or the array substrate, such as a liquid crystal display device, an organic EL device, a solid-state imaging device, and electronic paper. it can.

  Hereinafter, the colored photosensitive resin composition of the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And propylene glycol monomethyl ether acetate (136 g) in a solution obtained by adding 3.6 g of azobisisobutyronitrile to the flask from the dropping funnel over 2 hours, and further stirring at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a resin solution A-1 having a solid content acid value of 79 mgKOH / g (solid content: 35.1%). The weight average molecular weight in terms of polystyrene measured by GPC was 13,000, and the molecular weight distribution (Mw / Mn) was 2.1.

Synthesis example 2
An appropriate amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Next, using a dropping pump, 19 parts by weight of methacrylic acid and 171 parts by weight of epoxidized dicyclopentenyl acrylate (trade name “E-DCPA”, manufactured by Daicel Corporation) were added to the flask with propylene glycol monomethyl ether acetate 40 The solution dissolved in parts by weight was added dropwise over about 5 hours. On the other hand, using another dropping pump, a solution prepared by dissolving 26 parts by weight of the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitryl) in 120 parts by weight of propylene glycol monomethyl ether acetate was taken over about 5 hours. And dropped into the flask. After dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a resin solution A-2 having a solid content of 43.5 wt%. The produced copolymer had a weight average molecular weight of 8000 for Mw and a degree of dispersion of 1.98.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured under the following conditions using the GPC method.
Apparatus: K2479 (manufactured by Shimadzu Corporation)
Column: SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector: RI
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Example 1
[Preparation of curable composition 1]
Pigment: C.I. I. 40 parts of Pigment Red 254,
15 parts of acrylic pigment dispersant,
32 parts of resin solution A-1 and 200 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
232 parts of resin solution A-1
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 40 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF Japan Ltd.) 6.6 parts,
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 2.7 parts,
Solvent: 426 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain curable composition 1.

Example 2
[Preparation of curable composition 2]
Pigment: C.I. I. Pigment Green 58 35 parts,
7.0 parts of an acrylic pigment dispersant,
40 parts of resin solution A-1 and 169 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Pigment: C.I. I. 20 parts of Pigment Yellow 138,
2.9 parts of acrylic pigment dispersant,
20 parts of resin solution A-1 and 91 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
134 parts of resin solution A-1
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 43 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
8.5 parts,
Solvent: 440 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain curable composition 2.

Example 3
[Preparation of curable composition 3]
Pigment: C.I. I. Pigment Blue 15: 6 32 parts,
9.5 parts of acrylic pigment dispersant,
24 parts of resin solution A-1 and 145 parts of propylene glycol monomethyl ether acetate were mixed, and a pigment dispersion in which the pigment was sufficiently dispersed using a bead mill,
247 parts of resin solution A-1
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 41 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 14 parts of bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819; manufactured by BASF Japan Ltd.)
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 6.8 parts,
Solvent: 477 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 parts, manufactured by Toray Dow Corning Co., Ltd.
Were mixed to obtain a curable composition 3.

Example 4
[Preparation of curable composition 4]
Resin solution A-1 353 parts,
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 83 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
3.1 parts
Solvent: 561 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain curable composition 4.

Example 5
[Preparation of curable composition 5]
Pigment: C.I. I. 40 parts of Pigment Red 254,
15 parts of acrylic pigment dispersant,
26 parts of resin solution A-2 and 207 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
187 parts of resin solution A-2,
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 40 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure 907; manufactured by BASF Japan Ltd.) 6.6 parts,
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 2.7 parts,
Solvent: 471 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain curable composition 5.

Example 6
[Preparation of curable composition 6]
Pigment: C.I. I. Pigment Green 58 35 parts,
7.0 parts of an acrylic pigment dispersant,
32 parts of resin solution A-2 and 176 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
Pigment: C.I. I. 20 parts of Pigment Yellow 138,
2.9 parts of acrylic pigment dispersant,
16 parts of resin solution A-2 and 95 parts of propylene glycol monomethyl ether acetate,
And a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
99 parts of resin solution A-1
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 43 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
8.5 parts,
Solvent: 464 parts of propylene glycol monomethyl ether acetate, and Surfactant: Polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain curable composition 6.

Example 7
[Preparation of curable composition 7]
Pigment: C.I. I. Pigment Blue 15: 6 32 parts,
9.5 parts of acrylic pigment dispersant,
19 parts of resin solution A-2 and 150 parts of propylene glycol monomethyl ether acetate were mixed, and a pigment dispersion in which the pigment was sufficiently dispersed using a bead mill,
199 parts of resin solution A-2,
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 41 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
2.7 parts,
Polymerization initiator: 14 parts of bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide (Irgacure 819; manufactured by BASF Japan Ltd.)
Polymerization initiation aid: diethylthioxanthone (KAYACURE DETX Nippon Kayaku Co., Ltd.) 6.8 parts,
Solvent: 525 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 parts, manufactured by Toray Dow Corning Co., Ltd.
Were mixed to obtain a curable composition 7.

Example 8
[Preparation of curable composition 8]
285 parts of resin solution A-2,
Polymerizable compound: Denacol acrylate DA-111
(Manufactured by Nagase ChemteX): 83 parts,
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE-01; manufactured by BASF Japan Ltd.)
3.1 parts
Solvent: 629 parts of propylene glycol monomethyl ether acetate, and surfactant: polyether-modified silicone oil (Tore Silicone SH8400;
0.02 part of Toray Dow Corning Co., Ltd.) was mixed to obtain a curable composition 8.

Comparative Example 9
[Preparation of curable composition 9]
Pigment: C.I. I. Pigment Green 36 5.51 parts Pigment: C.I. I. Pigment Yellow 150 2.43 parts Polyester pigment dispersant 1.20 parts Resin Solution A-1 8.77 parts and propylene glycol monomethyl ether acetate 37.63 parts are mixed and the pigment is sufficiently dispersed using a bead mill. Pigment dispersion,
Binder resin: 10 parts of resin solution A-1
Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.71 parts,
Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369; manufactured by BASF Japan Ltd.) 1.46 parts,
Photopolymerization initiator: 4,4-di (N, N-diethylamino) -benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.) 0.49 parts,
Additive: Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd.)
0.61 part, and solvent: propylene glycol monomethyl ether acetate 26.19 parts,
Were mixed to obtain a curable composition 9.

<Pattern preparation>
A PET film (Toray Lumirror 75-T60) was bonded onto a 2-inch square glass plate to prepare a substrate. The curable composition was applied on the PET film side of the substrate by spin coating, dried under reduced pressure at an ultimate pressure of 66 Pa, and then pre-baked on a hot plate at 60 ° C. for 2 minutes. After allowing to cool, the distance between the substrate coated with the curable composition and the quartz glass photomask is set to 150 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). Note that a photomask having a line and space pattern of 10 to 100 μm was used. After irradiation with light, the pattern was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 40 seconds and washing with pure water. Got. Further, a cured pattern was obtained by heating (post-baking) at the temperature shown in Table 1 for 5 minutes. It was 2 micrometers when the film thickness of the obtained pattern or the hardened pattern was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Solvent resistance evaluation>
1 ml of propylene glycol monomethyl ether acetate is dropped on the pattern formed on the substrate or the cured pattern, and after standing still for 30 seconds, the spin coater is used to rotate at a rotation speed of 1000 rpm for 10 seconds, thereby propylene glycol monomethyl on the pattern. The ether acetate was shaken off.
The film thickness retention was calculated from the film thickness values measured before and after contact with propylene glycol monomethyl ether acetate according to the following formula. The higher the film thickness retention rate, the better the curability, and color mixing can be prevented when producing a color filter. The results are shown in Table 1.
(Thickness retention) (%) = (film thickness after contact) / (film thickness before contact)

<Resolution evaluation>
The obtained pattern was observed with a laser microscope (manufactured by Axio Imager MAT Carl Zeiss), and the minimum dimension resolved was taken as the resolution. The higher the resolution, the higher definition color filter can be produced. The results are shown in Table 1.

<Development unevenness evaluation>
The obtained pattern was observed with a laser microscope (Axio Imager MAT, Carl Zeiss). A pattern having no water spots on the pattern was ○ (development unevenness was not seen), and a pattern having water spots was x (development unevenness). Can be seen). When development unevenness is observed, color unevenness occurs when used for manufacturing a color filter.

<Cross cut test>
About the obtained coating film, the tape peeling test (cross cut test) according to JIS K5600-5-6 was performed, and adhesiveness with PET film was evaluated. The results are shown in Tables 1 and 2.

  According to this invention, the photosensitive resin composition which can form a pattern at low temperature can be provided. The pattern thus obtained can be suitably used as a color filter used in display devices such as liquid crystal display panels, electroluminescence panels, plasma display panels, and electronic paper.

Claims (7)

A photosensitive resin composition comprising a binder resin (A), a polymerizable compound (B) represented by the following formula (I), and a polymerization initiator (C).
<Formula (I)>

(R ₁ represents a hydrogen atom or a methyl group, X represents —R ₂ —O—R ₃ —, R ₂ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₃ represents a hydroxyl group. Represents an alkylene group having 1 to 3 carbon atoms) The photosensitive resin composition according to claim 1, wherein the polymerization initiator (C) is a polymerization initiator having a structure represented by the following formula (II).

(In the formula, each * represents a bond.) The photosensitive resin composition according to claim 1 or 2, wherein the polymerizable compound represented by (I) is a compound represented by the following formula (III).

  The photosensitive resin composition according to any one of claims 1 to 3, wherein the binder resin (A) contains any one of a vinyltoluene skeleton, a tricyclodecane skeleton, and a dicyclopentadiene skeleton.   Furthermore, the photosensitive resin composition in any one of Claims 1-4 containing a coloring agent (D).   The pattern formed with the photosensitive resin composition in any one of Claims 1-5.   A display device comprising the pattern according to claim 6.