JP2011022557A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition with the excellent coating property so as to form a pattern with the excellent resolution. <P>SOLUTION: The photosensitive resin composition includes (A) a silicon-containing acrylic resin, (B) a siloxane compound (excluding (A)), (C) a photosensitive substance and (D) a solvent. The (D) solvent includes (D1) an organic solvent having an ester bond and an ether bond but not a hydroxy group, and (D2) an organic solvent having a hydroxy group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition.

  In recent years, many display elements represented by liquid crystal displays and organic EL displays have been developed and put into practical use. In order to produce patterns included in these display elements, various photosensitive resin compositions have been proposed, for example, containing an organosilicon polymer, an acid generator and an organic solvent, and the organic solvent is methyl isobutyl ketone. the photosensitive resin composition is disclosed is (Patent Document 1).

JP-A-4-107561

  However, the applicability of the photosensitive resin composition including the organosilicon polymer, the acid generator, and the organic solvent and the resolution of the pattern formed from the photosensitive resin composition are not always sufficient. It was not satisfactory. The subject of this invention is providing the photosensitive resin composition which can form the pattern excellent in applicability | paintability and excellent in resolution.

［式（I）中、Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、−Ｏ−（ＣＨ_２）_ｗ−、−Ｃ（＝Ｏ）−Ｏ−（ＣＨ_２）_ｗ−または−（ＣＨ_２）_ｗ−を表し、Ｒ^２に含まれる−ＣＨ_２−は、ヘテロ原子で置換されていてもよい。ｗは、０〜８の整数を表す。
Ｒ^３〜Ｒ^１１は、それぞれ独立に、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数６〜１２のアリール基又は炭素数７〜１２のアラルキル基を表し、該脂肪族炭化水素基、該アリール基及び該アラルキル基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
ｙは、１〜５の整数を表し、ｘ及びｚは、それぞれ独立に、０〜５の整数を表す。］
［８］ケイ素含有アクリル樹脂（Ａ）が、少なくとも、ケイ素原子を有する非加水分解性重合性不飽和化合物（Ａ１）と、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種（Ａ２）とを重合してなる共重合体を含有するケイ素含有アクリル樹脂である前記［６］又は［７］記載の感光性樹脂組成物。
［９］ケイ素含有アクリル樹脂（Ａ）が、さらに（Ａ１）及び（Ａ２）と共重合可能な単量体（Ａ３）（ただし、（Ａ１）及び（Ａ２）を除く）を重合してなる共重合体を含有するケイ素含有アクリル樹脂である前記［８］記載の感光性樹脂組成物。
［１０］シロキサン化合物（Ｂ）（ただし、（Ａ）を除く）が、式（II）で表されるモノマーに由来する構造単位を含む化合物である前記［１］〜［９］のいずれか記載の感光性樹脂組成物。

Ｒ^１２ _ｎＳｉ（ＯＲ^１３）_４−ｎ （II）

［式（II）中、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数６〜１２のアリール基又は炭素数７〜１２のアラルキル基を表し、該脂肪族炭化水素基、アリール基及びアラルキル基の水素原子は、重水素原子、フッ素原子、塩素原子、シアノ基、ヒドロキシ基、炭素数１〜４のアルコキシ基、アミノ基、スルファニル基、オキシラニル基、アクリロイル基又はメタクリロイル基で置換されていてもよい。ｎは、０〜３の整数を表す。ｎが２以下の整数である場合、Ｒ^１３は、それぞれ同一であっても異なる種類の基であってもよい。ｎが２以上の整数である場合、Ｒ^１２は、それぞれ同一であっても異なる種類の基であってもよい。］
［１１］感光物質（Ｃ）が光酸発生剤である前記［１］〜［１０］のいずれか記載の感光性樹脂組成物。
［１２］熱硬化促進剤（Ｅ）を含有する前記［１］〜［１１］のいずれか記載の感光性樹脂組成物。
［１３］前記［１］〜［１２］のいずれか記載の感光性樹脂組成物を用いて形成されるパターン。
［１４］前記［１３］記載のパターンを含む表示素子。 The present invention provides the following [1] to [14].
[1] Contains a silicon-containing acrylic resin (A), a siloxane compound (B) (excluding (A)), a photosensitive material (C) and a solvent (D), and the solvent (D) is an ester bond and an ether. The photosensitive resin composition which is a solvent containing the organic solvent (D1) which has a bond and does not have a hydroxyl group, and the organic solvent (D2) which has a hydroxyl group.
[2] The photosensitive resin composition according to the above [1], wherein the organic solvent (D2) having a hydroxy group is an organic solvent having a boiling point of 100 to 200 ° C. at 1 atm.
[3] The photosensitivity according to [1] or [2], wherein the solvent (D) is an organic solvent (D3) having an ether bond and not having an ester bond and a hydroxy group. Resin composition.
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the organic solvent (D1) having an ester bond and an ether bond and having no hydroxy group is propylene glycol monomethyl ether acetate. object.
[5] The photosensitive resin composition according to the above [3], wherein the organic solvent (D3) having an ether bond and not having an ester bond and a hydroxy group is diethylene glycol dialkyl ether.
[6] The above [1] to [1], wherein the silicon-containing acrylic resin (A) is a silicon-containing acrylic resin containing at least a structural unit derived from the non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom. 5] The photosensitive resin composition in any one of.
[7] The photosensitive resin composition according to [6], wherein the non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom is a compound represented by the formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents —O— (CH ₂ ) _w —, —C (═O) —O— (CH ₂ ) _w — or — (CH ₂ ) _w —, and —CH ₂ — contained in R ² represents , May be substituted with a heteroatom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, The hydrogen atom contained in the hydrogen group, the aryl group and the aralkyl group may be substituted with a halogen atom.
y represents an integer of 1 to 5, and x and z each independently represents an integer of 0 to 5. ]
[8] The silicon-containing acrylic resin (A) is at least selected from the group consisting of a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom, an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The photosensitive resin composition according to the above [6] or [7], which is a silicon-containing acrylic resin containing a copolymer obtained by polymerizing one type (A2).
[9] A copolymer obtained by polymerizing a monomer (A3) (excluding (A1) and (A2)) that is copolymerizable with the silicon-containing acrylic resin (A) and (A1) and (A2). The photosensitive resin composition according to the above [8], which is a silicon-containing acrylic resin containing a polymer.
[10] Any one of [1] to [9] above, wherein the siloxane compound (B) (excluding (A)) is a compound containing a structural unit derived from the monomer represented by the formula (II). Photosensitive resin composition.

R ¹² _n Si (OR ¹³ ) _4-n (II)

[In Formula (II), R ¹² and R ¹³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. The hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group is deuterium atom, fluorine atom, chlorine atom, cyano group, hydroxy group, alkoxy group having 1 to 4 carbon atoms, amino group, sulfanyl group , An oxiranyl group, an acryloyl group or a methacryloyl group may be substituted. n represents an integer of 0 to 3. When n is an integer of 2 or less, R ¹³ may be the same or different groups. When n is an integer of 2 or more, R ¹² may be the same or different groups. ]
[11] The photosensitive resin composition according to any one of [1] to [10], wherein the photosensitive material (C) is a photoacid generator.
[12] The photosensitive resin composition according to any one of [1] to [11], which contains a thermosetting accelerator (E).
[13] A pattern formed using the photosensitive resin composition according to any one of [1] to [12].
[14] A display element comprising the pattern according to [13].

  According to the photosensitive resin composition of the present invention, it is possible to form a pattern having excellent coatability and excellent resolution.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention contains a silicon-containing acrylic resin (A).

  The silicon-containing acrylic resin (A) used in the photosensitive resin composition of the present invention is an acrylic resin containing a silicon atom, and is, for example, a polymer of acrylic acid ester or methacrylic acid ester.

  The silicon-containing acrylic resin (A) preferably contains at least a structural unit derived from a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom (hereinafter sometimes referred to as “(A1)”). The silicon-containing acrylic resin is preferably a silicon-containing acrylic resin containing a copolymer formed by polymerization with a monomer copolymerizable with (A1).

  (A1) is a compound which has a silicon atom and is non-hydrolyzable, that is, does not contain a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyloxy group or an acyloxy group), and is polymerizable unsaturated A compound containing a bond.

［式（I）中、Ｒ^１は、水素原子又はメチル基を表す。
Ｒ^２は、−Ｏ−（ＣＨ_２）_ｗ−、−Ｃ（＝Ｏ）−Ｏ−（ＣＨ_２）_ｗ−または−（ＣＨ_２）_ｗ−を表し、Ｒ^２に含まれる−ＣＨ_２−は、ヘテロ原子で置換されていてもよい。ｗは、０〜８の整数を表す。
Ｒ^３〜Ｒ^１１は、それぞれ独立に、炭素数１〜１２の１価の脂肪族炭化水素基、炭素数６〜１２のアリール基又は炭素数７〜１２のアラルキル基を表し、該脂肪族炭化水素基、該アリール基及び該アラルキル基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
ｙは、１〜５の整数を表し、ｘ及びｚは、それぞれ独立に、０〜５の整数を表す。］ (A1) is preferably a compound represented by the following formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents —O— (CH ₂ ) _w —, —C (═O) —O— (CH ₂ ) _w — or — (CH ₂ ) _w —, and —CH ₂ — contained in R ² represents , May be substituted with a heteroatom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, The hydrogen atom contained in the hydrogen group, the aryl group and the aralkyl group may be substituted with a halogen atom.
y represents an integer of 1 to 5, and x and z each independently represents an integer of 0 to 5. ]

R ¹ is a hydrogen atom or a methyl group.
Examples of R ² include a single bond, —CO—O—, —O—;
Methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3 -Alkanediyl group such as diyl group, butane-1,2-diyl group;
_{-O-CH 2 -, - O} -C 2 H 4 -, - O-C 3 H 6 -, - S-CH 2 -, - S-C 2 H 4 -, - S-C 3 H 6 -, Examples include heteroatom-containing alkanediyl groups such as —NH—CH ₂ —, —NH—C ₂ H ₄ —, and —NH—C ₃ H ₆ —. Among them, preferably a single bond, a methylene group, an ethylene _{group, * - O-CH 2 -} , * - O-C 2 H 4 -, * - C (= O) -O-CH 2 -, * - C (= O) —O—C ₂ H ₄ —, * —C (═O) —O—C ₃ H ₆ — (* represents a bond to C).

R ^{3 to} R ¹¹ can be selected from monovalent groups that are non-hydrolyzable. As such a non-hydrolyzable group, any group selected from the group consisting of a non-polymerizable group and a polymerizable group can be selected. In the present specification, a non-hydrolyzable group means that a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyloxy group, or an acyloxy group) is stably present as it is without being hydrolyzed under the condition that the hydrolyzable group is hydrolyzed. A group having the property of

Examples of R ^{3 to} R ¹¹ include carbon number 1 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl, sec-butyl group, tert-butyl group, octyl group, and dodecyl group. ~ 12 aliphatic hydrocarbon groups;
Aryl groups such as phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl;
Examples include aralkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group. Preferred examples of R ^{3 to} R ¹¹ include a methyl group, an ethyl group, a phenyl group, a pentafluorophenyl group, a trifluoromethylphenyl group, a bis (trifluoromethyl) phenyl group, and more preferably a methyl group and a phenyl group. Can be mentioned.

  Examples of (A1) include (trimethylsilylmethyl) methacrylate, (phenyldimethylsilyl) methyl methacrylate, 1- (3-methacryloyloxypropyl) -1,1,3,3,3-pentamethyldisiloxane, 1- ( 3-methacryloyloxypropyl) polydimethylsiloxane, 3-acryloyloxypropylmethylbis (trimethylsiloxy) silane, 3-methacryloyloxypropyltris (trimethylsiloxy) silane, tert-butyldimethylvinylsilane, allyldimethylsilane, allyltrimethylsilane, tri Phenylvinylsilane, trimethylsilyl methacrylate, vinyldiethylmethylsilane, vinyltris (trimethylsiloxy) silane, vinyltrimethylsilane, vinylmethylbis (trimethyl Rushirokishi) silane, phenyl dimethyl vinyl silane, and the like phenylmethyl vinyl silane. These may be used singly or in combination of two or more.

  Examples of (A1) include FM-0711 (Mw: 1000, Formula (I-1)), FM-0721 (Mw: 5000, Formula (I-1)), FM-0725 (Mw: 10,000, Formula ( I-1)), FM-0701 (Mw: 420, formula (I-1)), FM-0701T (Mw: 420, formula (I-2)) (all manufactured by Chisso Corporation), X- 22-174DX (Mw: 4600, Formula (I-1)), X-24-8201 (Mw: 2100), X-22-2426 (Mw: 12000, Formula (I-1)), X-22-2404 Commercial products such as (Mw: 420, formula (I-2)) and X-22-2406 (both manufactured by Shin-Etsu Chemical Co., Ltd.) may be used.

［式（I−１）中、Ｒ^８、ｗおよびｙは、前記と同じ意味を表す。］

[In formula (I-1), R ⁸ , w and y represent the same meaning as described above. ]

  Examples of the monomer copolymerizable with (A1) include unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (A2) (hereinafter sometimes referred to as “(A2)”), which contains silicon. The acrylic resin (A) is preferably a silicon-containing acrylic resin containing at least a copolymer obtained by polymerizing (A1) and (A2).

  In (A2), the unsaturated carboxylic acid is a carboxylic acid having an unsaturated bond, and the unsaturated carboxylic acid anhydride is a carboxylic acid anhydride having an unsaturated bond.

Examples of (A2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic 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) acryloyloxy of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Alkyl] esters;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used from the viewpoint of high copolymerization reactivity and high solubility in an aqueous alkali solution. These can be used alone or in combination of two or more. In the present specification, (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid.

  Further, the silicon-containing acrylic resin (A) is a monomer (A3) copolymerizable with (A1) and (A2) (excluding (A1) and (A2), hereinafter referred to as “(A3)”). It is preferable that it is a silicon-containing acrylic resin containing a copolymer obtained by polymerizing.

  (A3) is preferably a compound having an unsaturated bond and at least one group selected from the group consisting of an epoxy group, an oxetanyl group, an active methylene group and an active methine group. For example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 3- (meth) acryloxymethyloxetane, 3-methyl-3- ( (Meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-phenyl-3- (meth) acryloxymethyloxetane, 2-trifluoromethyl-3- (meth) acryloxymethyloxetane 2-pentafluoroethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3 -(Meth) acryloxyethyl oxetane, - trifluoromethyl-3- (meth) acryloxy ethyl oxetane or 2-pentafluoroethyl-3- (meth) acryloxy ethyl oxetane and the like. Among these, preferably 3- (meth) acryloxymethyloxetane, 3-methyl-3- (meth) acryloxymethyloxetane, 3-ethyl-3- (meth) acryloxymethyloxetane, 2-phenyl-3- (meth) ) Acryloxymethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxymethyl oxetane, 2-pentafluoroethyl-3- (meth) acryloxymethyl oxetane, 3-methyl-3- (meth) acryloxyethyl Oxetane, 3-methyl-3- (meth) acryloxyethyl oxetane, 2-phenyl-3- (meth) acryloxyethyl oxetane, 2-trifluoromethyl-3- (meth) acryloxyethyl oxetane or 2-pentafluoro ethyl-3- (meth) acryloxy ethyl oxetane can be mentioned .

  The compound having an epoxy group and an unsaturated bond is preferably a compound having a structure obtained by epoxidizing a cyclic olefin and having an unsaturated bond. Examples of the cyclic olefin include dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclononene, bicycloundecene, tricycloundecene, bicyclododecene, and tricyclododecene. Compounds having 8 to 12 carbon atoms are preferred. More preferably, at least one compound selected from the group consisting of a compound represented by the following formula (III) and a compound represented by formula (IV) can be mentioned.

［式（III）及び式（IV）中、Ｒは、水素原子又はヒドロキシ基で置換されていてもよい炭素数１〜４の脂肪族炭化水素基を表す。
Ｘは、単結合又はヘテロ原子を含んでいてもよい炭素数１〜６のアルキレン基を表す。
］

[In formula (III) and formula (IV), R represents a C1-C4 aliphatic hydrocarbon group which may be substituted with a hydrogen atom or a hydroxy group.
X represents a C1-C6 alkylene group which may contain a single bond or a hetero atom.
]

Examples of R include aliphatic hydrocarbon groups such as a hydrogen atom, 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;
Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1- (hydroxymethyl) ethyl group, 1-hydroxy-1-methyl Examples thereof include hydroxy group-containing aliphatic hydrocarbon groups such as an ethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. Among them, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

X is, for example, an alkylene group such as a single bond, a methylene group, an ethylene group, or a propylene group;
_{-O-CH 2 -, - O} -C 2 H 4 -, - O-C 3 H 6 -, - S-CH 2 -, - S-C 2 H 4 -, - S-C 3 H 6 -, Examples include heteroatom-containing alkylene groups such as —NH—CH ₂ —, —NH—C ₂ H ₄ —, and —NH—C ₃ H ₆ —. Among them, preferred are a single bond, a methylene group, an ethylene group, —O—CH ₂ — * and —O—C ₂ H ₄ — *, and more preferred are a single bond and —O—C ₂ H ₄ — *. (* Represents a bond with O).

Examples of the compound represented by the formula (III) include compounds represented by the formula (III-1) to the formula (III-15). Among them, preferably the formula (III-1), the formula (III-3), the formula (III-5), the formula (III-7), the formula (III-9), the formula (III-11) to the formula (III- The compound represented by 15) is mentioned, More preferably, the compound represented by Formula (III-1), Formula (III-7), Formula (III-9), and Formula (III-15) is mentioned.

  Examples of the compound represented by the formula (IV) include compounds represented by the formula (IV-1) to the formula (IV-15). Among them, preferably the formula (IV-1), the formula (IV-3), the formula (IV-5), the formula (IV-7), the formula (IV-9), the formula (IV-11) to the formula (IV- 15), and more preferably compounds represented by formula (IV-1), formula (IV-7), formula (IV-9), and formula (IV-15).

At least one compound selected from the group consisting of a compound represented by formula (III) and a compound represented by formula (IV) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio (compound represented by formula (III)) :( compound represented by formula (IV)), preferably 5:95 to 95: 5,
More preferably, it is 10: 90-90: 10, Most preferably, it is 20: 80-80: 20.

The active methylene group refers to —CH ₂ — having a carbonyl group at an adjacent position and having a reaction activity with respect to a nucleophile, and the active methine group refers to —CH (−) — similar to the active methylene group. Say. The compound having at least one group selected from the group consisting of an active methylene group and an active methine group and an unsaturated bond is a divalent group represented by the formula (Va) or 1 represented by the formula (Vb). A compound having a valent group and an unsaturated bond is preferred.
^{-X a -CHR k -X b -R m} (Va)
^{-X c -CHR n -X d (Vb} )
[In Formula (Va) and Formula (Vb), R ^k , R ^m and R ⁿ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ^k and R ^m are bonded to each other to form a ring. You may do it. X ^a , X ^b and X ^c each independently represent —CO—, * —CO—O—, —SO— or —SO ₂ —. X ^d represents a nitro group or a cyano group. * Represents a bond with C. ]

Examples of the compound having at least one group selected from the group consisting of the active methylene group and the active methine group and an unsaturated bond are represented by formulas (V-1) to (V-18). .
Compound etc. are mentioned. Among these, 2- (methacryloyloxy) ethyl acetoacetate represented by the formula (V-1) is preferable.

  The silicon-containing acrylic resin (A) further includes other copolymerizable monomer (A4) (excluding (A1), (A2) and (A3). Hereinafter, it may be referred to as “(A4)”. .) Can be a silicon-containing acrylic resin containing a copolymer obtained by polymerizing.

Examples of (A4) 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;
Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decan-8-yl (meth) acrylate (In this technical field, it is called dicyclopentanyl (meth) acrylate as a common name.
), (Meth) acrylic acid cyclic alkyl esters such as dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate;
(Meth) acrylic acid aryl 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 [2.2 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-di (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Cyclounsaturated 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 , Vinyl compounds such as isoprene and 2,3-dimethyl-1,3-butadiene.
Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These can be used alone or in combination of two or more.

  As described above, the silicon-containing acrylic resin (A) is preferably a silicon-containing acrylic resin containing at least a structural unit derived from (A1), more preferably (A1), (A1), and It is a silicon-containing acrylic resin containing a copolymer obtained by polymerizing a copolymerizable monomer, preferably (A2). Moreover, the structural unit derived | led-out from (A3) and also the structural unit derived | led-out from (A4) may be contained as needed.

When the silicon-containing acrylic resin (A) is composed only of structural units derived from (A1) and (A2), the ratio of the structural units derived from (A1) and (A2) in the silicon-containing acrylic resin (A) is The total number of moles of structural units constituting the copolymer is preferably in the following range.
Structural unit derived from (A1); 50 to 95 mol%
Structural unit derived from (A2); 5 to 50 mol%

When the silicon-containing acrylic resin (A) contains structural units derived from (A3) and (A4) in addition to the structural units derived from (A1) and (A2), the silicon-containing acrylic resin (A) is It is preferable that the ratio of the structural units derived from (A1) to (A4) is in the following range with respect to the total number of moles of the structural units constituting the copolymer.
Structural unit derived from (A1); 5-75 mol%
Structural unit derived from (A2); 5 to 50 mol%
Structural unit derived from (A3); 0 to 85 mol%
Structural unit derived from (A4); 0 to 50 mol%

  When the ratio of the structural units is within the above range, the compatibility between the silicon-containing acrylic resin (A) and the siloxane compound (B) (excluding (A)) tends to be good, and during development, Film reduction is unlikely to occur, and the non-pixel portion has good omissibility during development, and the resolution tends to be good.

  The silicon-containing acrylic resin (A) can be obtained by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972). And the cited references described in the literature. Specifically, a predetermined amount of a compound such as (A1) and (A2) constituting the copolymer, a polymerization initiator, and a solvent are charged into a reaction vessel, and stirred, heated, and kept warm in the absence of oxygen due to nitrogen substitution. By doing so, a polymer is obtained. In addition, the obtained copolymer may use the solution after the reaction as it is, may use a concentrated or diluted solution, and is taken out as a solid (powder) by a method such as reprecipitation. May be used.

  The weight average molecular weight in terms of polystyrene of the silicon-containing acrylic resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight-average molecular weight of the silicon-containing acrylic resin (A) is in the above range, the coating property tends to be good, the film is not easily reduced during development, and the non-pixel part is easily removed during development. The resolution tends to be good.

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

The content of the silicon-containing acrylic resin (A) is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the solid content in the photosensitive resin composition. When the content of the silicon-containing acrylic resin (A) is in the above range, the heat resistant light transmittance tends to be further improved. Here, solid content means the quantity remove | excluding the solvent from the photosensitive resin composition whole quantity.
In this specification, the heat resistant light transmittance refers to the rate of change of light transmittance in the visible light region before and after heating when a coating film containing the photosensitive resin composition is heated.

The photosensitive resin composition of the present invention contains a siloxane compound (B) (excluding (A)). The siloxane compound (B) (excluding (A)) is preferably a compound having a silicon atom to which a hydrolyzable group is bonded. The compound having a silicon atom to which a hydrolyzable group is bonded refers to a compound that forms a silanol compound by elimination of the hydrolyzable group under acidic or basic conditions. Examples of the hydrolyzable group include an alkoxy group, an alkoxycarbonyloxy group, and an acyloxy group.
The siloxane compound (B) (excluding (A)) is preferably a compound containing a structural unit derived from a monomer represented by the following formula (II).

R ¹² _n Si (OR ¹³ ) _4-n (II)

[In Formula (II), R ¹² and R ¹³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. The hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group is deuterium atom, fluorine atom, chlorine atom, cyano group, hydroxy group, alkoxy group having 1 to 4 carbon atoms, amino group, sulfanyl group , May be substituted with an oxiranyl group or a (meth) acryloyl group. n represents an integer of 0 to 3. When n is an integer of 2 or less, R ¹³ may be the same or different groups. When n is an integer of 2 or more, R ¹² may be the same or different groups. ]

  The siloxane compound (B) (excluding (A)) is an oligomer, polymer or mixture thereof containing a structural unit derived from the monomer represented by the formula (II).

R ¹² and R ¹³ include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, and their deuterium substitutes as an aliphatic hydrocarbon group, and a phenyl group and a biphenyl group as an aryl group. , Naphthyl groups, and their respective deuterium, fluorine, or chlorine substituents, and aralkyl groups include tolyl groups, xylyl groups, mesityl groups, and their deuterated products, fluorides, and chlorides. Among them, methyl group, 3,3,3-trifluoropropyl group, trideuteriomethyl group, trifluoromethylphenyl group, bis (trifluoromethyl) phenyl group phenyl group, pentafluorophenyl group, pentadeuteriophenyl group, Particularly preferred are a methyl group and a phenyl group.
Hydrogen atoms of the aliphatic hydrocarbon group, aryl group and aralkyl group are deuterium atom, fluorine atom, chlorine atom, cyano group, hydroxy group, alkoxy group having 1 to 4 carbon atoms, amino group, sulfanyl group, oxiranyl group Alternatively, it may be substituted with a (meth) acryloyl group.
The amino group may have a substituent. Examples of the substituent include an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an alkylidene group having 2 to 8 carbon atoms. And a cycloalkylidene group having 3 to 12 carbon atoms, and the hydrogen atom contained in these substituents may be substituted with an amino group. Specific examples of the amino group having a substituent include an N-methylamino group, an N, N′-dimethylamino group, an N-propylamino group, an N- (3-aminopropyl) amino group, and an N-cyclohexylamino group. Group, N-phenylamino group, N- (1-methylbutylidene) amino group, N- (1-methylpentylidene) amino group and the like.

  Examples of the monomer represented by the formula (II) include alkoxysilanes and silane coupling agents. Specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrakis (2-methacryloyloxyethoxy) silane, tetrakis (2-acryloyloxyethoxy) silane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, triethylsilane, benzyltrimethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, xylyltrimethoxysilane, (trifluoromethylphenyl) trimethoxysilane, biphenyltrimethoxysilane, diphenyldimethoxysilane, vinyltri Toxisilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane and the like.

  Examples of the siloxane compound (B) (excluding (A)) include organopolysiloxane resins. Organopolysiloxane resins are roughly classified into methylpolysiloxane resins and methylphenylpolysiloxane resins.

As the methylpolysiloxane resin, generally a copolymer having a three-dimensional network structure formed by combining structural units of SiO ₂ , CH ₃ SiO _3/2 , (CH ₃ ) ₂ SiO, and (CH ₃ ) ₃ SiO _1/2 is used. Can be mentioned.

The methylphenyl polysiloxane resin, typically _{SiO 2, CH 3 SiO 3/2,} C 6 H 5 SiO 3/2, (CH 3) 2 SiO, (C 6 H 5) 3 SiO 3/2, (CH 3 ) ₃ SiO _1/2 , (C ₆ H ₅ ) (CH ₃ ) SiO, (C ₆ H ₅ ) ₂ SiO, a copolymer having a three-dimensional network structure formed by combining structural units.
Methylphenylpolysiloxane resin has higher heat resistance than methylpolysiloxane resin.

  Examples of the organopolysiloxane resin include KR-242A, KC-89, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, X-40-9227, X -40-9247, KR-251, KR-400, KR-401N, KR-510, KR-9218, KR-217, X-41-1053, X-41-1056, X-41-1805, X-41 -1810, X-40-2651, X-40-2655A, KR-271, KR-282, KR-300, KR-311, KR-212, KR-213, KR-400, KR-255, ES-1001N , ES-1002T, ES-1023, ES-5206, ES-5230, ES-5235, ES-9706 (all are Shin-Etsu Chemical Co., Ltd. Etsu Chemical Co., Ltd.) may be a commercially available product, such as.

The silanol content of the siloxane compound (B) is preferably 1% or less. In this specification, the silanol content is the absorbance ratio of the absorption peak by 3500 cm ⁻¹ OH group (silanol-derived group) and 1271 cm ⁻¹ silicon-methyl group by infrared spectroscopy, that is, Abs (3500 cm ^−1. ) / Abs (1271 cm ⁻¹ ).

  The content of the siloxane compound (B) is a mass fraction with respect to the solid content in the photosensitive resin composition (referred to as a solid at 25 ° C. among the components in the composition), preferably 20 90 wt%, more preferably from 40 to 80 wt%. When the content of the siloxane compound (B) is in the above range, the heat resistant light transmittance tends to be further improved.

  By including the silicon-containing acrylic resin (A) and the siloxane compound (B) (excluding (A)), the heat-resistant light transmittance of the photosensitive resin composition of the present invention is improved.

  The photosensitive resin composition of the present invention contains a photosensitive substance (C). Examples of the photosensitive material (C) include a photoacid generator and a photobase generator, and a photoacid generator is preferred.

  Photoacid generators include nonionic compounds and ionic compounds.

  Examples of the nonionic compound include a halogen-containing compound, a diazoketone compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a sulfonimide compound, and a sulfonebenzotriazole compound.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4, Examples include 6-bis (trichloromethyl) -s-triazine.

  Examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Preferred diazo ketone compounds include ester compounds of 1,2-naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid and 2,3,4,4′-tetrahydroxybenzophenone, 1,2 -Ester compound of naphthoquinonediazide-5-sulfonic acid or 1,2-naphthoquinonediazide-4-sulfonic acid and 1,1,1-tris (4-hydroxyphenyl) ethane, 1,2-naphthoquinonediazide-5-sulfone Estes of acid or 1,2-naphthoquinonediazide-4-sulfonic acid with 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] diphenol Is mentioned.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

  Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryl disulfone compounds, and the like. Preferred examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl-4-methylphenyldisulfone compound, and the like.

  Examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate. Preferred examples include benzoin tosylate, pyrogallol trimesylate, trobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, and the like. As iminosulfonate, for example, PAI-101 (manufactured by Midori Chemical Co., Ltd.), PAI-106 (manufactured by Midori Chemical Co., Ltd.), CGI-1311 (manufactured by Ciba Japan Co., Ltd.) can be used.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl). Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl Reimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoro methylsulfonyloxy) -7-oxabicyclo 2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl Imido, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 Ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyl N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2 2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyl Imido, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [ 2.2.1] Heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2. 2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4 -Methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfide) Nyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) Examples include naphthyl dicarboxylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

  Examples of the sulfonebenzotriazole compound include 1-trifluoromethanesulfonyloxybenzotriazole, 1-nonafluorobutylsulfonyloxybenzotriazole, 1- (4-methylphenylsulfonyloxy) -benzotriazole, and the like.

As an ionic compound, what is comprised from the onium cation and the anion derived from a Lewis acid or a proton acid can be used.
Examples of the onium cation include diphenyliodonium, bis (p-tolyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p -Octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, triphenylsulfonium, tris (p-tolyl) Sulfonium, tris (p-isopropylphenyl) sulfonium, tris (2,6-dimethylphenyl) sulfonium, tris (p-tert-butylphenyl) sulfonium, tris (p-cyano) Enyl) sulfonium, tris (p-chlorophenyl) sulfonium, dimethyl (methoxy) sulfonium, dimethyl (ethoxy) sulfonium, dimethyl (propoxy) sulfonium, dimethyl (butoxy) sulfonium, dimethyl (octyloxy) sulfonium, dimethyl (octadecanoxy) sulfonium, Dimethyl (isopropoxy) sulfonium, dimethyl (tert-butoxy) sulfonium, dimethyl (cyclopentyloxy) sulfonium, dimethyl (cyclohexyloxy) sulfonium, dimethyl (fluoromethoxy) sulfonium, dimethyl (2-chloroethoxy) sulfonium, dimethyl (3-bromo Propoxy) sulfonium, dimethyl (4-cyanobutoxy) sulfonium, dimethyl (8-nitrooctyl) Oxy) sulfonium, dimethyl (18-trifluoromethyl octadecanoic oxy) sulfonium, dimethyl (2-hydroxy-isopropoxyphenyl) sulfonium, or dimethyl (tris (trichloromethyl) methyl) sulfonium and the like. Among them, preferable onium cations include bis (p-tolyl) iodonium, (p-tolyl) (p-isopropylphenyl) iodonium, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium or tris (p-tert-). Butylphenyl) sulfonium and the like.

  Examples of the anion derived from Lewis acid include hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and tetrakis (pentafluorophenyl) borate. Examples of the anion derived from a protonic acid include methanesulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate, camphorsulfonate, and the like. Preferable anions derived from Lewis acid or protonic acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate. The onium cation and the anion derived from Lewis acid or proton acid can be arbitrarily combined.

Examples of the ionic compound include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, bis (p-octylphenyl) iodonium hexafluorophosphate. Bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoro Phosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate DOO, methyl naphthyl hexafluorophosphate, ethyl naphthyl iodonium hexafluorophosphate;
Triphenylsulfonium hexafluorophosphate, tris (p-tolyl) sulfonium hexafluorophosphate, tris (p-isopropylphenyl) sulfonium hexafluorophosphate, tris (2,6-dimethylphenyl) sulfonium hexafluorophosphate, tris (p-tert- Butylphenyl) sulfonium hexafluorophosphate, tris (p-cyanophenyl) sulfonium hexafluorophosphate, tris (p-chlorophenyl) sulfonium hexafluorophosphate, dimethylnaphthylsulfonium hexafluorophosphate, diethylnaphthylsulfonium hexafluorophosphate, dimethyl (methoxy) sulfonium Hexafluorophosphate, dimethyl (ethoxy) Rufonium hexafluorophosphate, dimethyl (propoxy) sulfonium hexafluorophosphate, dimethyl (butoxy) sulfonium hexafluorophosphate, dimethyl (octyloxy) sulfonium hexafluorophosphate, dimethyl (octadecanoxy) sulfonium hexafluorophosphate, dimethyl (isopropoxy) sulfonium Hexafluorophosphate, dimethyl (tert-butoxy) sulfonium hexafluorophosphate, dimethyl (cyclopentyloxy) sulfonium hexafluorophosphate, dimethyl (cyclohexyloxy) sulfonium hexafluorophosphate, dimethyl (fluoromethoxy) sulfonium hexafluorophosphate, dimethyl (2-chloro Toxi) sulfonium hexafluorophosphate, dimethyl (3-bromopropoxy) sulfonium hexafluorophosphate, dimethyl (4-cyanobutoxy) sulfonium hexafluorophosphate, dimethyl (8-nitrooctyloxy) sulfonium hexafluorophosphate, dimethyl (18-trifluoro) Methyloctadecanoxy) sulfonium hexafluorophosphate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluorophosphate, dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluorophosphate;
Diphenyliodonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroarsenate, bis (p-tert-butylphenyl) iodonium hexafluoroarsenate, bis (p-octylphenyl) iodonium hexafluoroarsenate, bis (p -Octadecylphenyl) iodonium hexafluoroarsenate, bis (p-octyloxyphenyl) iodonium hexafluoroarsenate, bis (p-octadecyloxyphenyl) iodonium hexafluoroarsenate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroarsenate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, methylnaphthyl iodonium Oxafluoroarsenate, ethyl naphthyl iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (p-tolyl) sulfonium hexafluoroarsenate, tris (p-isopropylphenyl) sulfonium hexafluoroarsenate, tris (2, 6-dimethylphenyl) sulfonium hexafluoroarsenate, tris (p-tert-butylphenyl) sulfonium hexafluoroarsenate, tris (p-cyanophenyl) sulfonium hexafluoroarsenate, tris (p-chlorophenyl) sulfonium hexafluoroarsenate , Dimethylnaphthylsulfonium hexafluoroarsenate, diethylnaphthylsulfonium hexafluoroarsenate Dimethyl (methoxy) sulfonium hexafluoroarsenate, dimethyl (ethoxy) sulfonium hexafluoroarsenate, dimethyl (propoxy) sulfonium hexafluoroarsenate, dimethyl (butoxy) sulfonium hexafluoroarsenate, dimethyl (octyloxy) sulfonium hexafluoroarsenate , Dimethyl (octadecanoxy) sulfonium hexafluoroarsenate, dimethyl (isopropoxy) sulfonium hexafluoroarsenate, dimethyl (tert-butoxy) sulfonium hexafluoroarsenate, dimethyl (cyclopentyloxy) sulfonium hexafluoroarsenate, dimethyl (cyclohexyloxy) ) Sulfonium hexafluoroarsenate, dimethyl (Fluoromethoxy) sulfonium hexafluoroarsenate, dimethyl (2-chloroethoxy) sulfonium hexafluoroarsenate, dimethyl (3-bromopropoxy) sulfonium hexafluoroarsenate, dimethyl (4-cyanobutoxy) sulfonium hexafluoroarsenate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroarsenate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroarsenate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroarsenate, dimethyl (tris (trichloromethyl) Methyl) sulfonium hexafluoroarsenate;
Diphenyliodonium hexafluoroantimonate, bis (p-tolyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, bis (p-octylphenyl) iodonium hexafluoroantimonate, bis (p -Octadecylphenyl) iodonium hexafluoroantimonate, bis (p-octyloxyphenyl) iodonium hexafluoroantimonate, bis (p-octadecyloxyphenyl) iodonium hexafluoroantimonate, phenyl (p-octadecyloxyphenyl) iodonium hexafluoroantimonate Nate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, methyl naphthalate Tyl iodonium hexafluoroantimonate, ethyl naphthyl iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tolyl) sulfonium hexafluoroantimonate, tris (p-isopropylphenyl) sulfonium hexafluoroantimonate, tris ( 2,6-dimethylphenyl) sulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, tris (p-cyanophenyl) sulfonium hexafluoroantimonate, tris (p-chlorophenyl) sulfonium hexafluoro Antimonate, dimethyl naphthylsulfonium hexafluoroantimonate, diethyl naphthyl Rufonium hexafluoroantimonate, dimethyl (methoxy) sulfonium hexafluoroantimonate, dimethyl (ethoxy) sulfonium hexafluoroantimonate, dimethyl (propoxy) sulfonium hexafluoroantimonate, dimethyl (butoxy) sulfonium hexafluoroantimonate, dimethyl (octyl) Oxy) sulfonium hexafluoroantimonate, dimethyl (octadecanoxy) sulfonium hexafluoroantimonate, dimethyl (isopropoxy) sulfonium hexafluoroantimonate, dimethyl (tert-butoxy) sulfonium hexafluoroantimonate, dimethyl (cyclopentyloxy) sulfonium hexafluoro Antimonate, dimethyl (cyclohexyl) Ruoxy) sulfonium hexafluoroantimonate, dimethyl (fluoromethoxy) sulfonium hexafluoroantimonate, dimethyl (2-chloroethoxy) sulfonium hexafluoroantimonate, dimethyl (3-bromopropoxy) sulfonium hexafluoroantimonate, dimethyl (4-cyano Butoxy) sulfonium hexafluoroantimonate, dimethyl (8-nitrooctyloxy) sulfonium hexafluoroantimonate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium hexafluoroantimonate, dimethyl (2-hydroxyisopropoxy) sulfonium hexafluoroantimonate , Dimethyl (tris (trichloromethyl) methyl) sulfonium hexafluoro Nchimoneto;
Diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (p-tolyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, bis (p-octylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate, bis (P-octyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, bis (p-octadecyloxyphenyl) iodoniu Tetrakis (pentafluorophenyl) borate, phenyl (p-octadecyloxyphenyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, methylnaphthyliodonium tetrakis ( Pentafluorophenyl) borate, ethylnaphthyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, tris (p-tolyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-isopropylphenyl) Sulfonium tetrakis (pentafluorophenyl) borate, tris (2,6-dimethylphenyl) Rufonium tetrakis (pentafluorophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-cyanophenyl) sulfonium tetrakis (pentafluorophenyl) borate, tris (p-chlorophenyl) Sulfonium tetrakis (pentafluorophenyl) borate, dimethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, diethylnaphthylsulfonium tetrakis (pentafluorophenyl) borate, dimethyl (methoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (ethoxy) sulfonium tetrakis (Pentafluorophenyl) borate, dimethyl (propoxy) sulfonium teto Lakis (pentafluorophenyl) borate, dimethyl (butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (octadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (Isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tert-butoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclopentyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (cyclohexyloxy) sulfonium tetrakis ( Pentafluorophenyl) borate, dimethyl (fluorometh) Ii) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-chloroethoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (3-bromopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (4-cyanobutoxy) Sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (8-nitrooctyloxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (18-trifluoromethyloctadecanoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (2-hydroxy) Isopropoxy) sulfonium tetrakis (pentafluorophenyl) borate, dimethyl (tris (trichloromethyl) ) Methyl) sulfonium tetrakis (pentafluorophenyl) borate;
Diphenyliodonium trifluoromethanesulfonate, bis (p-tolyl) iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, tris (p-tolyl) sulfonium trifluoromethanesulfonate, tris (p-isopropylphenyl) sulfonium trifluoromethanesulfonate, tris (2 , 6-Dimethylphenyl) sulfonium trifluoromethanesulfonate. Among them, preferably bis (p-tolyl) iodonium hexafluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, triphenylsulfonium hexafluoro Phosphate, tris (p-tert-butylphenyl) sulfonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluoroarsenate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroarsenate, bis (p-tert -Butylphenyl) iodonium hexafluoroarsenate, triphenylsulfonium hexafluoroarsenate, tris (pt-butylphenyl) Fonium hexafluoroarsenate, bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate , Triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) Iodonium tetrakis (pentafluorophenyl) borate, bis (p-tert-butylphenyl) iodonium, triphenylsulfonium tetrakis (pentaful Rophenyl) borate, tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like, more preferably bis (p-tolyl) iodonium hexafluoroantimonate, (p-tolyl) (p-isopropyl). Phenyl) iodonium hexafluoroantimonate, bis (p-tert-butylphenyl) iodonium hexafluoroantimonate, triphenylsulfonium hexafluoroantimonate, tris (p-tert-butylphenyl) sulfonium hexafluoroantimonate, bis (p- Tolyl) iodonium tetrakis (pentafluorophenyl) borate, (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) ) Borate, bis (p-tert-butylphenyl) iodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, or tris (p-tert-butylphenyl) sulfonium tetrakis (pentafluorophenyl) borate Etc.

  Examples of the photobase generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, oxime compounds, α-aminoacetophenone compounds, biimidazole compounds Etc.

  As the type of base generated by light irradiation, either an organic base or an inorganic base can be used, but the generation efficiency of the base by light irradiation, the polymerization reaction between the silicon-containing acrylic resin (A) and the siloxane compound (B) From the viewpoints of the catalytic effect of the base and the solubility of the polymer obtained by the polymerization reaction in a reaction solution, an α-aminoacetophenone compound or a biimidazole compound is preferable.

  Transition metal complexes include, for example, bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) oxy Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl ] Propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl) Oxy] carbonyl] phenylenediamine, bis [ (2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, etc. Is mentioned.

  Examples of α, α-dimethyl-3,5-dimethoxybenzylcarbamates include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl). −3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] he Samethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluene Diamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, etc. Can be mentioned.

  Examples of oxime compounds include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, and adipoyl acetone. Oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime, O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, a compound represented by the following formula (VI) (N-benzoyloxy -1- (4-phenylsulfanylphenyl) octane-1-one-2-imine) (IRGACURE OXE-01; manufactured by Ciba Japan Co., Ltd.) )), A compound represented by the following formula (VII), and the like, preferably a compound represented by the formula (VI).

  Examples of α-aminoacetophenone compounds include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane. -1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone 2- (2-methylbenzyl) -2 -Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methylbenzyl ) -2-Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpho Nophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4-morpholino) Phenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2,3-dimethylbenzyl) -2-dimethylamino-1- (4) -Morpholinophenyl) -butanone, 2- (2,4-dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (3-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-chlorobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (2-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (3-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone 2- (4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-methoxy) Benzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- And an oligomer of (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone.

  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 (trialkoxyphene) B) Biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a 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, and preferably 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole. 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole, 2,2′4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4,5-diphenyl-1,1′- Imidazole, and the like.

  Among them, as the photosensitive material (C) contained in the photosensitive resin composition of the present invention, it is possible to increase the curing rate of the exposed portion, suppress the film loss of the pattern during development, and improve the remaining film rate. An acid generator is preferred.

  The content of the photosensitive material (C) is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, based on the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B). . When the content of the photosensitive material (C) is in the above range, the photosensitive resin composition becomes highly sensitive, and the strength of the pixel portion formed using the photosensitive resin composition or the surface of the pixel is increased. There exists a tendency for smoothness to become favorable.

  The photosensitive resin composition of the present invention contains a solvent (D). The solvent (D) used in the photosensitive resin composition of the present invention is an organic solvent (D1) having an ester bond and an ether bond and having no hydroxy group (hereinafter referred to as “organic solvent (D1)”). And an organic solvent (D2) having a hydroxy group (hereinafter sometimes referred to as “organic solvent (D2)”).

  The organic solvent (D1) is an organic solvent having an ester bond and an ether bond and not having a hydroxy group, and in particular, having one ester bond and one or more ether bonds and having a hydroxy group. It is preferable that the organic solvent is not used.

  Examples of the organic solvent (D1) include ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, and diethylene glycol ethyl ether acetate. , Diethylene glycol-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, 3-methoxybutyl acetate, etc. Inside Also preferably include propylene glycol monomethyl ether acetate.

  The organic solvent (D2) is an organic solvent having a hydroxy group, such as methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether. , Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethanol, propanol, butanol, 3-methoxy-1-butanol, hexanol, cyclohexanol, diacetone alcohol , ethylene glycol, propylene glycol or glycerin.

Among the organic solvents (D2), those having a boiling point of 100 to 200 ° C. at 1 atmosphere are preferable. In particular, if the boiling point is too low, unevenness tends to occur in the coated film on the substrate, so that it is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, particularly 115 ° C. or higher. More preferred. Further, if the boiling point is too high, it tends to remain in the coating film when the solvent is removed by pre-baking, and unevenness tends to occur or the pattern tends to decrease during development. Furthermore, it is more preferable that it is 180 degrees C or less, especially 175 degrees C or less.
Specific examples of such an organic solvent (D2) include propylene glycol monomethyl ether, ethyl lactate, 3-methoxy-1-butanol, diacetone alcohol, and the like, and particularly preferably 3-methoxy- 1-butanol is mentioned.

  Further, the solvent (D) includes an organic solvent (D3) having an ether bond and not having an ester bond and a hydroxy group (hereinafter sometimes referred to as “organic solvent (D3)”). It is preferable that

  Examples of the organic solvent (D3) include diethyl ether, methyl ethyl ether, methyl di-n-propyl ether, diisopropyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, dimethyl dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di- n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl-n-propyl ether, diethylene glycol methyl n-butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n- Butyl ether, Ethylene glycol methyl-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl mono-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl -N-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetradiethylene glycol methyl ethyl ether, tetraethylene glycol methyl-n-butyl ether, tetraethylene glycol di-n-butyl ether, tetraethylene glycol methyl-n-hexyl ether Tetraethylene glycol di-n-butyl ether, propylene Glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl n-butyl ether, Dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl-n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol Methyl-n-butyl ether, tripropylene Glycol di-n-butyl ether, tripropylene glycol methyl-n-hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, tetradipropylene glycol methyl ethyl ether, tetrapropylene glycol methyl n-butyl ether, dipropylene glycol di -N-butyl ether, tetrapropylene glycol methyl-n-hexyl ether, tetrapropylene glycol di-n-butyl ether and the like. Among these, diethylene glycol dialkyl ether is preferable, and specifically, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether are preferable.

The organic solvents (D1), (D2) and (D3) can be used alone or in combination of two or more.
When the solvent (D) is only the organic solvents (D1) and (D2), the organic solvents (D1) and (D2) can be mixed and used at an arbitrary ratio. The mass fraction of the total amount of the solvent) is preferably in the following range.
Organic solvent (D1); 50 to 90% by mass (more preferably 50 to 80% by mass)
Organic solvent (D2): 10 to 50% by mass (more preferably 20 to 50% by mass)

When the solvent (D) contains the organic solvent (D1), (D2) and (D3), the organic solvent (D1), (D2) and (D3) can be mixed and used at an arbitrary ratio, The mixing ratio is a mass ratio (mass fraction relative to the total amount of solvent), and is preferably in the following range.
Organic solvent (D1): 10 to 80% by mass (more preferably 40 to 80% by mass)
Organic solvent (D2): 10 to 50% by mass (more preferably 10 to 40% by mass)
Organic solvent (D3): 10 to 80% by mass (more preferably 10 to 50% by mass)

  When the mixing ratio of each organic solvent is in the above range, it is preferable that unevenness hardly occurs in the coating film after coating on the substrate or the coating film after pre-baking.

  The solvent (D) is preferably composed only of the organic solvent described above, but may contain other organic solvents as long as the effects of the present invention are not impaired. Examples of such an organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. .

  Content of the solvent (D) in the photosensitive resin composition of this invention is a mass fraction with respect to the photosensitive resin composition, Preferably it is 40-90 mass%, More preferably, it is 60-85 mass%. When the content of the solvent (D) is in the above-mentioned range, it is applied when applied by a coating apparatus such as a spin coater, a slit & spin coater, a slit coater (sometimes called a die coater or a curtain flow coater), and an ink jet. The flatness tends to be good, and the film thickness tends not to be insufficient when a pattern or a coating film is formed.

  The photosensitive resin composition of this invention can contain a thermosetting accelerator (E). The thermosetting accelerator (E) is not particularly limited as long as it accelerates the dehydration condensation reaction of alkoxysilane in the presence of heat. Among them, an organic titanium-containing compound and an organic zircon compound are preferable.

Specific examples of the organic titanium-containing compound include tetraisopropoxy titanium (TPT; manufactured by Nippon Soda Co., Ltd.), tetra-n-butoxy titanium (TBT; manufactured by Nippon Soda Co., Ltd.), and tetrakis (2-ethylhexyloxy). Titanium (TOT; manufactured by Nippon Soda Co., Ltd.), titanium-i-propoxyoctylene glycolate (TOG; manufactured by Nippon Soda Co., Ltd.), di-i-propoxy bis (acetylacetonato) titanium (T-50; Nippon Soda Co., Ltd.), propanedioxytitanium bis (ethyl acetoacetate) (T-60; Nippon Soda Co., Ltd.), tri-n-butoxy titanium monostearate (TBSTA; Nippon Soda Co., Ltd.), Titanium stearate (S-151; manufactured by Nippon Soda Co., Ltd.), diisopropoxy titanium diisostearate (S-152; manufactured by Nippon Soda Co., Ltd.), ( 2-n-butoxycarbonylbenzoyloxy) tributoxytitanium (S-181; manufactured by Nippon Soda Co., Ltd.).
Moreover, D-20 (made by Shin-Etsu Chemical Co., Ltd.), D-25 (made by Shin-Etsu Chemical Co., Ltd.), D-30 (made by Shin-Etsu Chemical Co., Ltd.), B-1 (Nippon Soda Co., Ltd.) B-2 (Nippon Soda Co., Ltd.), B-3 (Nippon Soda Co., Ltd.), B-4 (Nippon Soda Co., Ltd.), B-5 (Nippon Soda Co., Ltd.) , B-6 (Nippon Soda Co., Ltd.), B-7 (Nippon Soda Co., Ltd.), B-8 (Nippon Soda Co., Ltd.), B-9 (Nippon Soda Co., Ltd.), B Commercial products such as -10 (manufactured by Nippon Soda Co., Ltd.) can also be used.

Examples of the organic zircon compound include tetra-1-butoxyzirconium-containing material (TBZR; manufactured by Nippon Soda Co., Ltd.), and a reaction product of tetrabutoxyzirconium (IV) and acetylacetone (ZR-181; Nippon Soda Co., Ltd.). Product), inclusion of a reaction product of tetrabutoxyzirconium and acetylacetone (ZAA; manufactured by Nippon Soda Co., Ltd.), and the like.
Commercial products such as ZR-151 (manufactured by Nippon Soda Co., Ltd.) can also be used.

  Content of a thermosetting accelerator (E) is a mass fraction with respect to the total amount of a silicon containing acrylic resin (A) and a siloxane compound (B), and is 0.5-20 mass%, More preferably, it is 1.0. -10 mass%. When the content of the thermosetting accelerator (E) is in the above range, the dissolution contrast is improved, so that the resolution and the pattern shape tend to be good, which is preferable.

  Moreover, if it is a grade which does not impair the effect of this invention, a photosensitizer (F) can be used. Examples of the photosensitizer (F) include benzophenone compounds, thioxanthone compounds, anthracene compounds, and the like. And specific examples thereof include the following compounds. These can be used alone or in combination of two or more.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

  Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done.

  Other examples include 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.

  Moreover, as a photosensitizer (F), the compound which has the group which can raise | generate the chain transfer described in the Japanese translations of PCT publication No. 2002-544205 can also be used. A compound having a group capable of causing chain transfer may be contained in the photosensitive resin composition as a constituent component of the copolymer. Examples of the compound having a group capable of causing chain transfer include compounds represented by the following formulas (5) to (10).

  The content of the photosensitizer (F) is preferably 0.01 to 50% by mass, more preferably 0.1 to 40%, based on the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B). % By mass.

Further, the photopolymerization initiation aid (G) can be used in combination with the photosensitive material (C). In this case, two or more photopolymerization initiation assistants can be used in combination.
Examples of the photopolymerization initiation aid (G) include amine compounds, carboxylic acid compounds, polyfunctional thiol compounds, and compounds represented by the following formula (VIII).

Examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine;
Methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, Aromatic amine compounds such as 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone) and 4,4′-bis (diethylamino) benzophenone can be mentioned.

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

  Examples of the polyfunctional thiol compound include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhiol. Glycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropioate Nate, pentaerythritol tetrakis (3-mercaptobutanoate), 1,4-bis (3-mercaptobutoxy) butane .

［式（VIII）中、環Ｘは、ハロゲン原子で置換されていてもよい炭素数６〜１２の芳香族環を表す。
Ｙは、酸素原子又は硫黄原子を表す。
Ｒ^１４は、炭素数１〜６の脂肪族炭化水素基を表す。
Ｒ^１５は、ハロゲン原子で置換されていてもよい炭素数１〜１２の脂肪族炭化水素基又はハロゲン原子で置換されていてもよいアリール基を表す。］

[In Formula (VIII), Ring X represents an aromatic ring having 6 to 12 carbon atoms which may be substituted with a halogen atom.
Y represents an oxygen atom or a sulfur atom.
R ¹⁴ represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
R ¹⁵ represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group which may be substituted with a halogen atom. ]

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Moreover, as a C6-C12 aromatic ring, a benzene ring, a naphthalene ring, etc. are mentioned, for example.

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

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

  Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and 1-methyl-n-. Propyl group, 2-methyl-n-propyl group, tert-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1 , 1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, n-hexyl group, cyclohexyl group, 1-chloro-n-butyl group, 2 -Chloro-n-butyl group, 3-chloro-n-butyl group and the like can be mentioned.

  Examples of the aryl group optionally substituted with a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromo Examples thereof include a phenyl group, a dibromophenyl group, a naphthyl group, a chloronaphthyl group, a dichloronaphthyl group, a bromonaphthyl group, and a dibromonaphthyl group.

As a compound represented by the formula (VIII), specifically, for example,
2-benzoylmethylene-3-methyl-naphtho [2,1-d] thiazoline, 2-benzoylmethylene-3-methyl-naphtho [1,2-d] thiazoline, 2-benzoylmethylene-3-methyl-naphtho [2] , 3-d] thiazoline, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline, 2- (1-naphthoylmethylene) -3-methylbenzothiazoline, 2- (2-naphthoylmethylene) -3 -Methyl-5-phenylbenzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline, 2 -(1-naphthoylmethylene) -3-methyl-5-fluorobenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-5 Chlorobenzothiazoline, 2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-5-bromobenzothiazoline, 2- (1-naphtho) Ylmethylene) -3-methyl-5-bromobenzothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene) -3-methyl-5-phenylbenzothiazoline, 2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline, 2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline, 2- (4-Bifenoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline, 2- (4-Bifenoylmethylene) -3-methyl-naphtho [1 2-d] thiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] thiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [1,2- d] thiazoline, 2-benzoylmethylene-3-methyl-naphtho [2,1-d] oxazoline, 2-benzoylmethylene-3-methyl-naphtho [1,2-d] oxazoline, 2-benzoylmethylene-3-methyl -Naphtho [2,3-d] oxazoline, 2- (2-naphthoylmethylene) -3-methylbenzoxazoline, 2- (1-naphthoylmethylene) -3-methylbenzoxazoline, 2- (2-naphthoyl) Methylene) -3-methyl-5-phenylbenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-phenylbenzoxa Zolin, 2- (2-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-fluorobenzoxazoline, 2- (2-naphthoylmethylene) ) -3-Methyl-5-chlorobenzoxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-chlorobenzoxazoline, 2- (2-naphthoylmethylene) -3-methyl-5-bromobenzo Oxazoline, 2- (1-naphthoylmethylene) -3-methyl-5-bromobenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3- Methyl-5-phenylbenzoxazoline, 2- (2-naphthoylmethylene) -3-methyl-naphtho [2,1-d] oxy Zoline, 2- (2-naphthoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, 2- (4-biphenoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline, 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-naphtho [2,1-d] oxazoline, 2- (P-Fluorobenzoylmethylene) -3-methyl-naphtho [1,2-d] oxazoline and the like.

  Among these, 2- (2-naphthoylmethylene) -3-methylbenzothiazoline represented by the following formula (VIII-1) and 2-benzoylmethylene-3-methyl-naphtho represented by the following formula (VIII-2) are preferable. And [1,2-d] thiazoline and 2- (4-biphenoylmethylene) -3-methyl-naphtho [1,2-d] thiazoline represented by the following formula (VIII-3).

  As the photopolymerization initiation assistant (G), an amine compound, a polyfunctional thiol, and a compound represented by the formula (VIII) are more preferable.

  The content of the photopolymerization initiation auxiliary (G) is preferably 0.01 to 50% by mass, more preferably 0.1 to 0.1%, based on the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B). 40% by mass. When the amount of the photopolymerization initiation aid (G) is within the above range, the sensitivity of the resulting photosensitive resin composition is further increased, and the productivity of the patterned substrate formed using the photosensitive resin composition is improved. It tends to improve.

  If necessary, the photosensitive resin composition of the present invention may be used in combination with additives such as fillers, other polymer compounds, leveling agents, antioxidants, ultraviolet absorbers, flocculants, and chain transfer agents. You can also.

  As the filler, for example, glass, silica, and alumina.

  Examples of other polymer compounds include curable resins such as epoxy resins and maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. Can do.

  As the leveling agent, a commercially available surfactant can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, and amphoteric surfactants. These can be used alone or in combination of two or more. 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. Etc. Specifically, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFac (manufactured by DIC Corporation), Florard (Manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.), etc. Can be used.

  Examples of the antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3). , 5-Di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2 , 4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2′-methyle Bis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di such -tert- butyl-4-methyl phenol.

  Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, and the like.

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

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

  Moreover, when the photosensitive resin composition of this invention is used as a coating film, it is preferable that the average transmittance | permeability of a coating film is 90% or more, and it is more preferable that it is 95% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer for a coating film having a thickness of 2 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured by. Thereby, the coating film excellent in transparency in the visible light region can be provided.

The photosensitive resin composition of this invention can be apply | coated on a base material as follows, for example, can perform photocuring and image development, and can form a coating film and a pattern.
First, this composition is applied onto a substrate (usually glass) or a layer made of a solid content of a previously formed photosensitive resin composition, and prebaked from the applied photosensitive resin composition layer to obtain a solvent or the like. The volatile components are removed to obtain a smooth coating film. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use a device such as a mask aligner or a stepper so that the entire exposed portion is uniformly irradiated with parallel light rays and the mask and the substrate are accurately aligned. Thereafter, the cured coating film is brought into contact with an alkaline aqueous solution to dissolve the non-exposed portion and developed, whereby the intended pattern shape is obtained. The developing method may be any of a liquid piling method, a dipping method, a spray method, and the like. Further, the substrate may be tilted at an arbitrary angle during development.
Examples of the coating method include spin coating, casting coating, roll coating, slit and spin coating, and slit coating. After application, the photosensitive resin composition layer is formed by volatilizing volatile components such as a solvent by heating after drying (prebaking) or drying under reduced pressure. Here, the temperature of heating is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The photosensitive resin composition layer contains almost no volatile component.
Moreover, the thickness of the said photosensitive resin composition layer is about 1-8 micrometers.

In addition, it is preferable to heat-process in order to accelerate the hardening of an exposed part after exposure.
The heating condition varies depending on the composition of the photosensitive resin composition, the type of additive, and the like, but is usually 30 to 200 ° C, preferably 50 to 150 ° C.

The developer used for development after patterning exposure is usually an aqueous solution containing an alkaline compound and a surfactant.
The alkaline compound may be either an inorganic alkaline compound or an organic alkaline compound. Examples of inorganic alkaline compounds include sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, and carbonic acid. Sodium, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, ammonia and the like can be mentioned.
Examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, and ethanolamine. Is mentioned. These inorganic and organic alkaline compounds can be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass.

The surfactant in the alkaline developer may be any of a nonionic surfactant, an anionic surfactant, or a cationic surfactant.
Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene Examples include ethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, and polyoxyethylene alkylamine.
Examples of the anionic surfactant include higher alcohol sulfates such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, and dodecyl sodium sulfate. And alkyl aryl sulfonates such as sodium naphthalene sulfonate.
Examples of the cationic surfactant include amine salts or quaternary ammonium salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride.
These surfactants can be used alone or in combination of two or more.
The concentration of the surfactant in the alkali developer is preferably in the range of 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass.

  After development, it is washed with water and, if necessary, post-baking at 100 to 300 ° C. for 10 to 60 minutes can be performed.

  By using the photosensitive resin composition of the present invention, a coating film or a pattern can be formed on the substrate or the color filter substrate through the above steps. This coating film or pattern is useful as a photospacer used for liquid crystals. Moreover, if a photomask for hole formation is used in patterning exposure to a dry coating film, a hole can be formed and it is useful as an interlayer insulation film. Furthermore, when exposing to a dry coating film, it is possible to form a transparent film only by full exposure and heat curing, or heat curing without using a photomask, this transparent film is useful as an overcoat, It can also be used for a touch panel.

  The photosensitive resin composition of the present invention can provide a cured resin having excellent heat-resistant light transmittance. Moreover, when the photosensitive resin composition of the present invention is used, a cured resin pattern having a desired shape can be easily formed, and a photo spacer, an insulating film, a protrusion for controlling liquid crystal alignment, an overcoat, and a colored pattern film. It can be used for forming a pattern film used in a display element device, such as a coating layer for adjusting the thickness, an optical waveguide material, and an optical switching material.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
Nitrogen was flowed at a rate of 0.02 L / min into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 300 parts of propylene glycol monomethyl ether acetate was added and heated to 90 ° C. with stirring. Next, 30 parts of methacrylic acid, 135 parts of 3-methacryloxypropyltris (trimethylsiloxy) silane [formula (Ia)], 180 parts of 2- (methacryloyloxy) ethylacetoacetate [formula (Va)], and A solution was prepared by dissolving in 160 parts of propylene glycol monomethyl ether acetate, and the solution was dropped into a flask kept at 90 ° C. using a dropping funnel. On the other hand, a solution prepared by dissolving 15 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 180 parts of propylene glycol monomethyl ether acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of dropping of the polymerization initiator solution, the temperature was maintained at 90 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature to obtain a solution of a copolymer (resin Aa) having a solid content of 35.0% and an acid value of 65 mg-KOH / g (in terms of solid content). The weight average molecular weight Mw of the obtained resin Aa was 9.9 × 10 ³ .

[Synthesis Example 2]
A 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer was flowed with nitrogen at a rate of 0.02 L / min to form a nitrogen atmosphere, and 180 parts of ethyl 3-ethoxypropionate and 120 parts of 3-methoxy-1-butanol were added. And heated to 90 ° C. with stirring. Next, 30 parts of methacrylic acid, 135 parts of 3-methacryloxypropyltris (trimethylsiloxy) silane [formula (Ia)], 180 parts of 2- (methacryloyloxy) ethylacetoacetate [formula (Va)], and A solution was prepared by dissolving in 96 parts of ethyl 3-ethoxypropionate and 64 parts of 3-methoxy-1-butanol, and the solution was dropped into a flask kept at 90 ° C. using a dropping funnel. On the other hand, a solution obtained by dissolving 15 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 108 parts of ethyl 3-ethoxypropionate and 72 parts of 3-methoxy-1-butanol was added dropwise. It was dripped in the flask over 4 hours using a funnel. After completion of dropping of the polymerization initiator solution, the temperature was maintained at 90 ° C. for 4 hours. Thereafter, the mixture was cooled to room temperature to obtain a solution of a copolymer (resin Ab) having a solid content of 35.2% and an acid value of 65 mg-KOH / g (in terms of solid content). The obtained resin Ab had a weight average molecular weight Mw of 1.5 × 10 ⁴ .

<Measurement of molecular weight>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin Aa and the resin Ab 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

[Example 1]
143 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (50 parts in terms of solid content), KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B), 20 parts, KC-89S (Shin-Etsu Chemical) Kogyo Co., Ltd.) (B) 30 parts, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (PI-2074; Rhodia) (C) 5 parts, 2,4-diethylthioxanthone (KAYACURE DETX-S; Nippon Kayaku Co., Ltd.) (F) 1.5 parts, D-20 (Shin-Etsu Chemical Co., Ltd.) (E) 4 parts, propylene glycol monomethyl ether A photosensitive resin composition 1 was obtained by mixing 30 parts of acetate (D1), 51 parts of diethylene glycol methyl ethyl ether (D3), and 31 parts of diacetone alcohol (D2). About the obtained photosensitive resin composition 1, the evaluation was performed by the following method.

<Pattern formation>
A 2-inch square glass substrate (Eagle 2000; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. On this glass substrate, the photosensitive resin composition 1 was applied by spin coating, and prebaked at 100 ° C. for 3 minutes in a clean oven.
After standing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere.
As a photomask, a photomask in which a 10 μm line and space pattern was formed was used. Moreover, at the time of light irradiation, it set so that the space | interval of the board | substrate which apply | coated the photosensitive resin composition 1 and a photomask might be set to 100 micrometers.
After light irradiation, it was baked on a hot plate at 100 ° C. for 5 minutes. After that, it was developed by immersing in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 80 seconds, washed with water, and then post-washed in an oven at 220 ° C. for 30 minutes. Baking was performed to obtain a pattern. The film thickness of the pattern obtained after standing to cool was 3.1 μm as measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Average transmittance of photosensitive resin composition>
About the photosensitive resin composition 1, the average transmittance | permeability (%) in 400-700 nm was measured using the ultraviolet visible spectrophotometer (V-650DS; JASCO Corporation make) (quartz cell, optical path length: 1 cm). did. The results are shown in Table 1.

<Average transmittance of coating film>
The same operation as described above was performed except that no photomask was used at the time of light irradiation, and a coating film was prepared so that the film thickness after post-baking became 2.0 μm. The average transmittance (%) at a wavelength of 400 to 700 nm of the prepared coating film was measured using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 1.

<Resolution evaluation>
When the obtained pattern was observed using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.), a 10 μm line and space pattern was resolved. When the 10 μm line and space pattern was resolved, it was judged that the resolution was good, and when it was not resolved, it was judged that the resolution was poor. The results are shown in Table 1 when the resolution is good.

<Radial unevenness evaluation>
The photosensitive resin composition 1 was applied to a silicon substrate on which 1 cm square dot patterns with a thickness of 1.5 μm were formed at intervals of 2 cm by spin coating so that the film thickness after pre-baking was 2.8 μm. Medium was pre-baked at 100 ° C. for 3 minutes. When the substrate was observed under a sodium lamp, no radial unevenness was observed. The case where radial unevenness was not recognized was judged as good applicability, and the case where radial unevenness was observed was judged as poor applicability. The results are shown in Table 1 with ◯ when the applicability is good.

<Amorphous unevenness evaluation>
The photosensitive resin composition 1 was applied onto a silicon substrate by spin coating so that the film thickness after pre-baking was 2.8 μm, and pre-baked at 100 ° C. for 3 minutes in a clean oven. When the substrate was observed under a sodium lamp, amorphous irregularities were not observed. When the amorphous unevenness was not recognized, the applicability was judged as good, and when the amorphous unevenness was found, the applicability was judged as poor. The results are shown in Table 1 with ◯ when the applicability is good.

<Thickness difference evaluation>
In the substrate obtained by performing the same operation as the amorphous unevenness evaluation, the film thicknesses at the edge and the center of the substrate were measured with a film thickness measuring device, and the difference was calculated. The result was good with a film thickness difference of 0.3 μm. The smaller the film thickness difference, the better the applicability.

[Example 2]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that diacetone alcohol was replaced with ethyl lactate and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that diacetone alcohol was replaced with 3-methoxy-1-butanol, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
A photosensitive resin composition was prepared in the same manner as in Example 1 except that diacetone alcohol was replaced with propylene glycol monomethyl ether, and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
KR-213 (Shin-Etsu Chemical Co., Ltd.) (B) 40 parts, KC-89S (Shin-Etsu Chemical Co., Ltd.) (B) 60 parts, 4-methylphenyl [4- (1-methylethyl) phenyl ] Iodonium tetrakis (pentafluorophenyl) borate (PI-2074; Rhodia) (C) 5 parts, 2,4-diethylthioxanthone (KAYACURE DETX-S; Nippon Kayaku Co., Ltd.) (F) 1.5 Part, D-20 (manufactured by Shin-Etsu Chemical Co., Ltd.) (E) 4 parts, and 100 parts of methyl isobutyl ketone were mixed to obtain a photosensitive resin composition. The evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 5]
143 parts of resin solution (A) containing resin Aa obtained in Synthesis Example 1 (50 parts in terms of solid content), KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B), 20 parts, KC-89S (Shin-Etsu Chemical) Kogyo Co., Ltd.) (B) 30 parts, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (PI-2074; Rhodia) (C) 5 parts, 2,4-diethylthioxanthone (KAYACURE DETX-S; Nippon Kayaku Co., Ltd.) (F) 1.5 parts, D-20 (Shin-Etsu Chemical Co., Ltd.) (E) 4 parts, propylene glycol monomethyl ether 50 parts of acetate (D1) and 62 parts of ethyl lactate (D2) were mixed to obtain a photosensitive resin composition. The obtained photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 6]
Example 5 was repeated except that 50 parts of propylene glycol monomethyl ether acetate (D1) and 62 parts of ethyl lactate (D2) were replaced with 30 parts of propylene glycol monomethyl ether acetate (D1) and 82 parts of ethyl lactate (D2). A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 7]
Example 5 was repeated except that 50 parts of propylene glycol monomethyl ether acetate (D1) and 62 parts of ethyl lactate (D2) were replaced with 10 parts of propylene glycol monomethyl ether acetate (D1) and 102 parts of ethyl lactate (D2). A photosensitive resin composition was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 8]
A photosensitive resin composition was prepared in the same manner as in Example 5 except that ethyl lactate was replaced with 3-methoxy-1-butanol (D2), and evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

[Example 9]
Example except that 50 parts of propylene glycol monomethyl ether acetate (D1) and 62 parts of ethyl lactate (D2) are replaced with 30 parts of propylene glycol monomethyl ether acetate (D1) and 82 parts of 3-methoxy-1-butanol (D2) A photosensitive resin composition was prepared in the same manner as in Example 5 and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 10]
Example except that 50 parts of propylene glycol monomethyl ether acetate (D1) and 62 parts of ethyl lactate (D2) are replaced with 10 parts of propylene glycol monomethyl ether acetate (D1) and 102 parts of 3-methoxy-1-butanol (D2) A photosensitive resin composition was prepared in the same manner as in Example 5 and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[Example 11]
143 parts of resin solution (A) containing resin Ab obtained in Synthesis Example 2 (50 parts in terms of solid content), KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B), 20 parts, KC-89S (Shin-Etsu Chemical) Kogyo Co., Ltd.) (B) 30 parts, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (PI-2074; Rhodia) (C) 5 parts, 2,4-diethylthioxanthone (KAYACURE DETX-S; manufactured by Nippon Kayaku Co., Ltd.) (F) 1.5 parts, D-20 (manufactured by Shin-Etsu Chemical Co., Ltd.) (E) 4 parts, 3-ethoxypropion 68 parts of ethyl acid (D1) and 45 parts of 3-methoxy-1-butanol (D2) were mixed to obtain a photosensitive resin composition. The obtained photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 12]
68 parts ethyl 3-ethoxypropionate (D1) and 45 parts 3-methoxy-1-butanol (D2), 89 parts ethyl 3-ethoxypropionate (D1) and 25 parts 3-methoxy-1-butanol (D2) A photosensitive resin composition was prepared in the same manner as in Example 11 except that it was changed to, and the evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

[Example 13]
68 parts of ethyl 3-ethoxypropionate (D1) and 45 parts of 3-methoxy-1-butanol (D2), 27 parts of ethyl 3-ethoxypropionate (D1), 62 parts of propylene glycol monomethyl ether acetate (D1) and 3 parts A photosensitive resin composition was prepared in the same manner as in Example 11 except that it was replaced with 25 parts of -methoxy-1-butanol (D2), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 14]
68 parts of ethyl 3-ethoxypropionate (D1) and 45 parts of 3-methoxy-1-butanol (D2), 48 parts of ethyl 3-ethoxypropionate (D1), 41 parts of propylene glycol monomethyl ether acetate (D1) and 3 parts A photosensitive resin composition was prepared in the same manner as in Example 11 except that it was replaced with 25 parts of -methoxy-1-butanol (D2), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[Example 15]
68 parts of ethyl 3-ethoxypropionate (D1) and 45 parts of 3-methoxy-1-butanol (D2), 27 parts of ethyl 3-ethoxypropionate (D1), 21 parts of propylene glycol monomethyl ether acetate (D1) and 3 parts A photosensitive resin composition was prepared in the same manner as in Example 11 except that it was replaced with 25 parts of -methoxy-1-butanol (D2), and evaluated in the same manner as in Example 1. The results are shown in Table 3.

  It turns out that the photosensitive resin composition of this invention is excellent in applicability | paintability, and the pattern which consists of the photosensitive resin composition of this invention is excellent in resolution. On the other hand, in the comparative example, excellent resolution and applicability could not be confirmed.

  According to the photosensitive resin composition of the present invention, a pattern having excellent resolution and unevenness can be suppressed, and a coating film having a uniform film thickness can be formed.

Claims (14)

  Contains silicon-containing acrylic resin (A), siloxane compound (B) (excluding (A)), photosensitive material (C) and solvent (D), and solvent (D) has an ester bond and an ether bond. And the photosensitive resin composition which is a solvent containing the organic solvent (D1) which does not have a hydroxyl group, and the organic solvent (D2) which has a hydroxyl group.   The photosensitive resin composition according to claim 1, wherein the organic solvent (D2) having a hydroxy group is an organic solvent having a boiling point of 100 to 200 ° C at 1 atm.   The photosensitive resin composition according to claim 1 or 2, wherein the solvent (D) is a solvent further comprising an organic solvent (D3) having an ether bond and not having an ester bond and a hydroxy group.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the organic solvent (D1) having an ester bond and an ether bond and having no hydroxy group is propylene glycol monomethyl ether acetate.   The photosensitive resin composition according to claim 3, wherein the organic solvent (D3) having an ether bond and not having an ester bond and a hydroxy group is diethylene glycol dialkyl ether.   The silicon-containing acrylic resin (A) is a silicon-containing acrylic resin containing a repeating unit derived from at least a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom. Photosensitive resin composition. The photosensitive resin composition according to claim 6, wherein the non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom is a compound represented by the formula (I).

[In Formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents —O— (CH ₂ ) _w —, —C (═O) —O— (CH ₂ ) _w — or — (CH ₂ ) _w —, and —CH ₂ — contained in R ² represents , May be substituted with a heteroatom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, The hydrogen atom contained in the hydrogen group, the aryl group and the aralkyl group may be substituted with a halogen atom.
y represents an integer of 1 to 5, and x and z each independently represents an integer of 0 to 5. ]   The silicon-containing acrylic resin (A) is at least one selected from the group consisting of a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom, an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride ( The photosensitive resin composition according to claim 6 or 7, which is a silicon-containing acrylic resin containing a copolymer obtained by polymerizing A2).   A copolymer obtained by polymerizing a monomer (A3) (but different from (A1) and (A2)) copolymerizable with (A1) and (A2), wherein the silicon-containing acrylic resin (A) The photosensitive resin composition according to claim 8, which is a silicon-containing acrylic resin containing The photosensitive resin composition according to claim 1, wherein the siloxane compound (B) (however, different from (A)) is a compound containing a structural unit derived from the monomer represented by the formula (II). object.

R ¹² _n Si (OR ¹³ ) _4-n (II)

[In Formula (II), R ¹² and R ¹³ are each independently a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. The hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group is deuterium atom, fluorine atom, chlorine atom, cyano group, hydroxy group, alkoxy group having 1 to 4 carbon atoms, amino group, sulfanyl group , An oxiranyl group, an acryloyl group or a methacryloyl group may be substituted. n represents an integer of 0 to 3. When n is an integer of 2 or less, R ¹³ may be the same or different groups. When n is an integer of 2 or more, R ¹² may be the same or different groups. ]   The photosensitive resin composition according to claim 1, wherein the photosensitive substance (C) is a photoacid generator.   The photosensitive resin composition in any one of Claims 1-11 containing a thermosetting accelerator (E).   The pattern formed using the photosensitive resin composition in any one of Claims 1-12.   A display element comprising the pattern according to claim 13.