JP5349159B2 - Photosensitive resin composition - Google Patents

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, photosensitive resin compositions comprising an alkali-soluble resin and a photopolymerization initiator are disclosed. (Patent Document 1).

Japanese Patent Laid-Open No. 11-133600

  However, the transmittance of the coating film using the photosensitive resin composition comprising the alkali-soluble resin and the photopolymerization initiator is not always satisfactory. The subject of this invention is providing the photosensitive resin composition which can form the coating film which has sufficient transmittance | permeability.

  As a result of studies to find a photosensitive resin composition capable of solving the above-mentioned problems, the present inventor has found that a silicon-containing acrylic resin (A), a siloxane compound (B) (excluding (A)), a photosensitive material ( It has been found that the transmittance of the formed coating film is improved by the photosensitive resin composition containing C) and having a moisture content of 0.15 to 0.45 mass% with respect to the photosensitive resin composition. The present invention has been reached.

［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−を表す。Ｒ^２に含まれるメチレン基は、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す。該脂肪族炭化水素基、アリール基及び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。］
［５］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／又は不飽和カルボン酸無水物（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［３］又は［４］記載の感光性樹脂組成物。
［６］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［５］記載の感光性樹脂組成物。
［７］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］〜［６］のいずれか記載の感光性樹脂組成物。

［式（II）中、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素数１〜１２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、メルカプト基、イミノ基、エポキシ基又は（メタ）ア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。］
［８］溶剤（Ｄ）を含む前記［１］〜［７］のいずれか記載の感光性樹脂組成物。
［９］前記［１］〜［８］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を含む表示素子。 That is, the present invention provides the following [1] to [9].
[1] Contains a silicon-containing acrylic resin (A), a siloxane compound (B) (excluding (A)) and a photosensitive material (C), and has a water content of 0.15 to 0.005. The photosensitive resin composition which is 45 mass%.
[2] The photosensitive resin composition according to the above [1], wherein the moisture content relative to the photosensitive resin composition is 0.19 to 0.41% by mass.
[3] The above [1] or [3], wherein 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. 2] The photosensitive resin composition of description.
[4] The photosensitive resin composition according to the above [3], 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 —. The methylene group contained in R ² may be substituted with a hetero atom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent an 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 aliphatic hydrocarbon group, aryl group and 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. ]
[5] The silicon-containing acrylic resin (A) contains at least a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom, and an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A2). The photosensitive resin composition according to the above [3] or [4], which is a silicon-containing acrylic resin containing a polymerized copolymer.
[6] 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 [5], which is a silicon-containing acrylic resin containing a polymer.
[7] Any of [1] to [6], 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.

[In the formula (II), R ¹² and R ¹³ each independently represent an 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 includes a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an amino group, a mercapto group, and an imino group. , An epoxy group or a (meth) acryloyl 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. ]
[8] The photosensitive resin composition according to any one of [1] to [7], including a solvent (D).
[9] A display element comprising a pattern formed using the photosensitive resin composition according to any one of [1] to [8].

  According to the photosensitive resin composition of the present invention, a coating film having excellent transmittance can be formed.

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 has at least a repeating 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 that has a silicon atom and is non-hydrolyzable, that is, does not contain a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyl group, a carboxy group, or the like). It is a compound containing a saturated 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−を表す。Ｒ^２に含まれるメチレン基は、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す。該脂肪族炭化水素基、アリール基及び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 —. The methylene group contained in R ² may be substituted with a hetero atom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent an 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 aliphatic hydrocarbon group, aryl group and 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, an ester bond, and an ether bond;
Methylene group, ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, 1-ethylethylene Group, alkylene group such as 2-ethylethylene group, etc .;
_{-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, preferably a single bond, a methylene group, an ethylene group, an oxymethylene group, an oxyethylene group, —C (═O) —O—CH ₂ —, —C (═O) —O—C ₂ H ₄ —, — C (═O) —O—C ₃ H ₆ — may be mentioned.

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 this specification, the non-hydrolyzable group is stably present as it is without being hydrolyzed under the condition that a hydrolyzable group (for example, an alkoxy group, an alkoxycarbonyl group or a carboxy group) is hydrolyzed. A group having properties.

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 and naphthyl;
Aralkyl groups such as a tolyl group, a xylyl group and a mesityl group can be mentioned. Preferred aliphatic hydrocarbon groups include methyl and ethyl groups, and preferred aryl groups include phenyl and pentafluorophenyl groups, more preferably phenyl groups. Further, preferred aralkyl groups include trifluoromethylphenyl and bis (trifluoromethyl) phenyl.

  Examples of (A1) include (trimethylsilylmethyl) methacrylate, (phenyldimethylsilyl) methyl methacrylate, 1- (3-methacryloxypropyl) -1,1,3,3,3-pentamethyldisiloxane, 1- ( 3-methacryloxypropyl) polydimethylsiloxane, 3-acryloxypropylmethylbis (trimethylsiloxy) silane, 3-methacryloxypropyltris (trimethylsiloxy) silane, tert-butyldimethylvinylsilane, allyldimethylsilane, allyltrimethylsilane, tri Phenylvinylsilane, trimethylsilyl methacrylate, vinyldiethylmethylsilane, vinyltris (trimethylsiloxy) silane, vinyltrimethylsilane, vinylmethylbis (trimethylsiloxy) silane, phenol Le dimethylvinylsilane, like phenylmethyl vinyl silane. These can be used alone 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;
Anhydrides of the aforementioned unsaturated dicarboxylic acids;
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 carboxyl group in the same molecule, such as α- (hydroxymethyl) acrylic acid. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used 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.

  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 And ethyl-3- (meth) acryloxyethyl oxetane .

  The compound having an epoxy group and an unsaturated bond is preferably a compound having an epoxy group on the ring of the aliphatic polycyclic compound and having an unsaturated bond. Examples of the aliphatic polycyclic compound include dicyclopentane, tricyclodecane, norbornane, isonorbornane, bicyclooctane, bicyclononane, bicycloundecane, tricycloundecane, bicyclododecane, and tricyclododecane. Compounds having a number of 8 to 12 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、水素原子又は水酸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 hydroxyl 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-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 3-hydroxy-n-propyl group, 1-hydroxy-isopropyl group, Hydroxyl-containing aliphatic hydrocarbons such as 2-hydroxy-isopropyl group, 1-hydroxy-n-butyl group, 2-hydroxy-n-butyl group, 3-hydroxy-n-butyl group, 4-hydroxy-n-butyl group Groups. 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;
Examples thereof include heteroatom-containing alkylene groups such as oxymethylene group, oxyethylene group, oxypropylene group, thiomethylene group, thioethylene group, thiopropylene group, aminomethylene group, aminoethylene group, and aminopropylene group. Of these, a single bond, a methylene group, an ethylene group, an oxymethylene group and an oxyethylene group are preferable, and a single bond and an oxyethylene group are more preferable.

  Examples of the 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. In the case of mixing, the mixing ratio is molar ratio (compound represented by formula (III)) :( compound represented by formula (IV)), preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, particularly preferably 20:80 to 80:20.

  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;
Alkyl acrylates 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, dicyclopenta Nyl (meth) acrylate), (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-carboxybicyclo [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-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6- Di (hydroxymethyl) bicyclo [2.2.1] hept-2-e 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-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Ethylbicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxy Carbonyl bicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (tert-butoxycarbonyl) bicyclo [2.2. 1] Bicyclo unsaturated compounds such as hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;
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 repeating 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 components derived from (A1) and (A2) in the silicon-containing acrylic resin (A) is When the total number of moles of the constituent components constituting the copolymer is 100 mol%, it is preferably in the following range in terms of mole fraction.
Structural units derived from (A1); 50-95 mol%
Structural unit derived from (A2); 5 to 50 mol%

When the silicon-containing acrylic resin (A) includes 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: The ratio of the constituent components derived from (A1) to (A4) may be in the following range in terms of mole fraction when the total number of moles of the constituent components constituting the copolymer is 100 mol%. preferable.
Structural units derived from (A1); 5-75 mol%
Structural unit derived from (A2); 5 to 50 mol%
Structural units derived from (A3); 0-85 mol%
Structural units derived from (A4); 0-50 mol%

  When the molar fraction of the constituent components 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, It is preferred that film loss is unlikely to occur during development, and that non-pixel portions are easily removed during development and 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, which is preferable.

  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, which is preferable.

The content of the silicon-containing acrylic resin (A) is preferably a mass fraction with respect to the solid content in the photosensitive resin composition (referred to solid at 25 ° C. among the components in the composition). Is 5 to 90 mass%, more preferably 10 to 70 mass%. 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, which is preferable.
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.

［式（II）中、Ｒ^１２及びＲ^１３は、それぞれ独立に、炭素数１〜１２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、メルカプト基、イミノ基、エポキシ基又は（メタ）ア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。］ 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 containing a structural unit derived from a monomer represented by the following formula (II).

[In the formula (II), R ¹² and R ¹³ each independently represent an 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 includes a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an amino group, a mercapto group, and an imino group. , An epoxy group or a (meth) acryloyl 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 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, xylyl, mesityl, and their deuterium, fluorine, and chloride. Among them, preferred aliphatic hydrocarbon groups are methyl group, 3,3,3-trifluoropropyl group, trideuteriomethyl group, and preferred aryl groups are phenyl group, pentafluorophenyl group, pentadeuteriophenyl group, especially Preferably, a phenyl group is mentioned as an aryl group. Preferred aralkyl groups include a trifluoromethylphenyl group and a bis (trifluoromethyl) phenyl group.
The hydrogen atom of the aliphatic hydrocarbon group, aryl group and aralkyl group includes a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an amino group, a mercapto group, and an imino group. , An epoxy group or a (meth) acryloyl group may be substituted.

  The monomer represented by the formula (II) represents, for example, an alkoxysilane or a silane coupling agent. Specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra (2-methacryloxyethoxy) silane, tetra (2-acryloxyethoxy) silane, tetrachlorosilane, tetraacetoxysilane, tetraaminosilane, methyltrimethoxy Silane, methyltrichlorosilane, methyldichlorosilane, methyldimethoxysilane, methyltriacetoxysilane, methyltriethoxysilane, methyltributoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoro Propyltriethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, trimethylmethoxysilane, triethylsilane, triethylchlorosilane, benzyltrimeth Sisilane, phenyltrimethoxysilane, phenylsilane, phenyltriacetoxysilane, phenyltriaminosilane, phenyltrichlorosilane, phenyltriethoxysilane, xylyltrimethoxysilane, trifluoromethylphenyltotimethoxysilane, biphenyltrimethoxysilane, biphenyltrichlorosilane, Diphenyldimethoxysilane, diphenyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino) Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Lysidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Examples include mercaptopropyltrimethoxysilane.

  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 It is -90 mass%, More preferably, it is 40-80 mass%. When the content of the siloxane compound (B) is in the above range, the heat resistant light transmittance tends to be further improved, which is preferable.

  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 material (C). Examples of the photosensitive material (C) include a photoacid generator and a photobase generator.

  Photoacid generators include nonionic compounds and ionic compounds.

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

  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 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. Preferred anions derived from Lewis acid include hexafluoroantimonate or tetrakis (pentafluorophenyl) borate. The onium cation and Lewis acid-derived anion can be arbitrarily combined.

Examples of the cationic polymerization initiator include diphenyliodonium hexafluorophosphate, bis (p-tolyl) iodonium hexafluorophosphate, bis (p-tert-butylphenyl) iodonium hexafluorophosphate, and bis (p-octylphenyl) iodonium hexafluoro. Phosphate, bis (p-octadecylphenyl) iodonium hexafluorophosphate, bis (p-octyloxyphenyl) iodonium hexafluorophosphate, bis (p-octadecyloxyphenyl) iodonium hexafluorophosphate, phenyl (p-octadecyloxyphenyl) iodonium hexa Fluorophosphate, (p-tolyl) (p-isopropylphenyl) iodonium hexafluorophos Eto, 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. 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 preferably used, but the generation efficiency of the base by light irradiation, polymerization of the silicon-containing acrylic resin (A) and the siloxane compound (B) From the viewpoint of the catalytic effect of the base in the reaction and the solubility of the polymer obtained by the polymerization reaction in the 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, acryloylacetophenone oxime, acryloylbenzophenone oxime, acryloylacetone oxime, O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one, compounds represented by the following formula (VI) (1,2- Octadione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (IRGACURE OXE-01; manufactured by Ciba Japan)), lower It includes such compounds represented by formula (VII), preferably compounds of the formula (VI).

  Examples of the α-aminoacetophenone compound include 2-benzyl-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 -Morpholinophenyl) -butanone, 2- (2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-propylbenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, -(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 -Methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-methyl-4-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (2-bromo-4-methoxybenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone oligomers and the like It is below.

  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.

  Content of a photosensitive material (C) is a mass fraction with respect to the total amount of a silicon-containing acrylic resin (A) and a siloxane compound (B), Preferably it is 0.1-40 mass%, More preferably, it is 1-30. % By mass. 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 and is preferable.

The photosensitive resin composition of the present invention may contain no solvent, but preferably contains a solvent (D). As the solvent (D), various organic solvents used in the field of the photosensitive resin composition can be used. Specifically, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether, propylene glycol methyl ether propionate, propylene glycol ethyl Propylene glycol alkyl ether propionates such as ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;
Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, and butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate;
Cyclic ethers such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

  Among the above-mentioned solvents, an organic solvent having a boiling point of 100 ° C. to 200 ° C. is preferable from the viewpoint of coating properties and drying properties, more preferably alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butane. Examples include diol monoalkyl ethers, esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, particularly preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, Mention is made of methoxybutanol, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These can be used alone or in admixture of two or more.

  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 60-90 mass%, More preferably, it is 70-85 mass%. When the content of the solvent (D) is within the above range, it is applied by a coating device such as a spin coater, slit & spin coater, slit coater (sometimes called a die coater or curtain flow coater), or an inkjet. The coating property is expected to be good, and is preferable.

  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. Of these, organic titanium-containing compounds and organic zircon compounds are preferred.

Specific examples of the organic titanium-containing compound include tetra-i-propoxy titanium (TPT; manufactured by Nippon Soda Co., Ltd.), tetra-n-butoxy titanium (TBT; manufactured by Nippon Soda Co., Ltd.), and tetrakis (2-ethylhexyl). Oxy) 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; manufactured by Nippon Soda Co., Ltd.), propanedioxytitanium bis (ethyl acetoacetate) (T-60; manufactured by Nippon Soda Co., Ltd.), tri-n-butoxy titanium monostearate (TBSTA; manufactured by Nippon Soda Co., Ltd.) ), Titanium stearate (S-151; manufactured by Nippon Soda Co., Ltd.), di-i-propoxytitanium diisostearate (S-152; manufactured by Nippon Soda Co., Ltd.), (2- and 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), Preferably it is 0.5-20 mass%, More preferably, it is 1 0.0 to 10% by mass.

  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. Specific examples 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).

  Content of a photosensitizer (F) is a mass fraction with respect to the total amount of a silicon-containing acrylic resin (A) and a siloxane compound (B), Preferably it is 0.01-50 mass%, More preferably, it is 0. .1 to 40% by mass.

Furthermore, the photopolymerization initiation assistant (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-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane It is.

［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 which may be substituted with a halogen atom include a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a dibromophenyl group, a chlorobromophenyl group, a biphenyl group, a chlorobiphenyl group, a dichlorobiphenyl group, and a bromo group. 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 assistant (G) is a mass fraction with respect to the total amount of the silicon-containing acrylic resin (A) and the siloxane compound (B), preferably 0.01 to 50% by mass, more preferably It is 0.1-40 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, which is preferable.

  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.

  Examples of the filler include 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 Kyoei Chemical Co., Ltd.), Ftop (manufactured by Tochem Products Co., Ltd.), MegaFac (Dainippon Ink Chemical Industries, Ltd.) Manufactured), FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by GENECA), EFKA (manufactured by EFKA CHEMICALS), PB821 (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 -Tert-butyl-4-methylphenol and the like.

  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.

  The moisture content in the photosensitive resin composition of this invention is 0.15-0.45 mass% with respect to the photosensitive resin composition, Preferably it is 0.19-0.41 mass%. In particular, if the water content is too high, the non-pixel portion removal property tends to deteriorate during development, and therefore, it is more preferably 0.41% by mass or less. Moreover, since it exists in the tendency for the light transmittance of the coating film in wavelength 400nm to fall when too low, it is more preferable that it is 0.19 mass% or more. The amount of moisture in the photosensitive resin composition can be measured using a Karl Fischer moisture meter.

  The amount of water in the photosensitive resin composition of the present invention includes the amount of water brought in from water contained in raw materials such as solvents, in addition to water positively added to the reaction system. For example, when the water content is adjusted by adding pure water, the silicon-containing acrylic resin (A) and the siloxane compound (B) are mixed when the silicon-containing acrylic resin (A) and the siloxane compound (B) are mixed. Photosensitivity having a water content within the above range by adding 0.1 to 3.0% by mass, preferably 0.5 to 2.5% by mass of pure water in a mass fraction with respect to the total amount. A resin composition can be obtained.

  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. % Or more is preferable, and 80% or more is more preferable.

  Further, when the photosensitive resin composition of the present invention is used as a coating film, the average transmittance of the coating film is preferably 90% or more, and more preferably 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 can be provided.

  Furthermore, the light transmittance of the coating film at a wavelength of 400 nm is preferably 90% or more, and more preferably 92% or more. Thereby, the coating film excellent in transparency can be provided. In particular, when the light transmittance of the coating film at a wavelength of 400 nm is lower than 90%, the color reproducibility of the pixel portion of the color filter is hindered by coloring of the coating film.

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. At this time, the thickness of the coating film is about 1 to 6 μm. 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 filling 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 1.5-8 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 photo spacer used in liquid crystal and organic EL display devices. 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 film used in a display 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 the dropwise addition of the polymerization initiator solution, the mixture was kept at 90 ° C. for 4 hours, and then cooled to room temperature, and the solid content was 35.0%, and the acid value was 65 mg-KOH / g (solid content conversion). A solution of coalescence (resin Aa) was obtained. The obtained resin Aa had a weight average molecular weight (Mw) of 9.9 × 10 ³ .

[Synthesis Example 2]
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, and 200 parts of 3-methoxy-1-butanol and 105 parts of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Next, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (III-a) and a formula (IV-a)) The compound is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 140 parts of 3-methoxybutyl acetate, and the solution is kept at 70 ° C. using a dropping funnel. The solution was dropped into the flask. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of 3-methoxybutyl acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The solid content was 32.6% and the acid value was 110 mg-KOH / g (solid content conversion). A solution of coalescence (resin Ab) was obtained. The obtained resin Ab had a weight average molecular weight (Mw) of 1.3 × 10 ⁴ .

<Measurement of molecular weight>
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resins Aa and Ab were measured using the GPC method under the following conditions.
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 (manufactured by Shin-Etsu Chemical Co., Ltd.) (B) 30 parts, 4-methylphenyl [4- (1-methylethyl) phenyl] iodonium tetrakis (pentafluorophenyl) borate (PI-2074; Rhodia) (C) 5 parts, 2,4-diethylthioxanthone (F) 1.5 parts, D-20 (Shin-Etsu Chemical Co., Ltd.) 4 parts (E), propylene glycol monomethyl ether acetate (D) The photosensitive resin composition 1 was obtained by mixing 228 parts and 0.5 parts of pure water. About the obtained photosensitive resin composition 1, the evaluation was performed by the following method.

<Moisture content of photosensitive resin composition>
About the photosensitive resin composition 1, the moisture content was measured by the Karl Fischer method. The results are shown in Table 2.

<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 cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), irradiate with light at an exposure amount of 100 mJ / cm ² (based on 365 nm) in an air atmosphere and bake at 100 ° C. for 5 minutes in a clean oven. did.
As a photomask, a photomask in which a pattern (having a LINE (rectangular) -shaped light-transmitting portion having a side of 10 μm and a spacing of the LINE (rectangular) shapes of 10 μm) is formed on the same plane is used. It was. At the time of light irradiation, the interval between the substrate coated with the photosensitive resin composition 1 and the quartz glass photomask was set to 100 μm.
After light irradiation, the film containing the photosensitive resin composition 1 was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 25 ° C. for 80 seconds, After washing with water, it was post-baked in an oven at 100 ° C. for 60 minutes. After standing to cool, when measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), the film thickness of the obtained film was 2.2 μm.

<Line width, cross-sectional shape>
Using a scanning electron microscope (S-4000; manufactured by Hitachi, Ltd.), the line width and shape (cross section) were observed and measured.
The line width measured in the pattern corresponding to each pattern of 10 μm on the photomask was 10.9 μm in the 10 μm portion. The cross-sectional shape was a forward taper with the pattern angle with respect to the substrate being less than 90 degrees. In addition, the case where the angle of the pattern with respect to a board | substrate was 90 degree | times or more was judged as reverse taper. A forward taper is preferred because the ITO wiring is less likely to break during the formation of the liquid crystal display device. The results are shown in Table 2 with a case where the taper is forward tapered.

<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 2.

<Average transmittance (%) of film at wavelength of 400 to 700 nm>
Except not using a photomask at the time of light irradiation, operation similar to the above was performed and the cured film was produced so that the film thickness after hardening might be set to 2.0 micrometers. The light transmittance (%) at an average transmittance (%) nm 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 2.

<Light transmittance at a wavelength of 400 nm of the film>
Except not using a photomask at the time of light irradiation, operation similar to the above was performed and the cured film was produced so that the film thickness after hardening might be set to 2 micrometers. The light transmittance (%) at a wavelength of 400 nm of the prepared coating film was measured using a microspectrophotometer (OSP-SP200; manufactured by OLYMPUS). The results are shown in Table 2.

[Examples 2 to 4 and Comparative Example 1]
A photosensitive resin composition was prepared in the same manner as in Example 1 so as to have the composition shown in Table 1, and evaluated in the same manner as in Example 1. The results are shown in Table 2.

  It turns out that the coating film which consists of the photosensitive resin composition of this invention is excellent in the transmittance | permeability in wavelength 400nm. On the other hand, in the comparative example, a coating film having sufficient transmittance at a wavelength of 400 nm could not be obtained.

  According to the photosensitive resin composition of the present invention, a coating film having excellent transmittance can be formed.

Claims (9)

Containing a silicon-containing acrylic resin (A), a siloxane compound (B) (excluding (A)) and a photosensitive material (C),
The photosensitive resin composition whose moisture content with respect to the photosensitive resin composition is 0.15-0.45 mass%.   The photosensitive resin composition according to claim 1, wherein the moisture content relative to the photosensitive resin composition is 0.19 to 0.41 mass%.   The photosensitivity according to claim 1 or 2, wherein the silicon-containing acrylic resin (A) is a silicon-containing acrylic resin containing at least a repeating unit derived from a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom. Resin composition. The photosensitive resin composition according to claim 3, 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 —. The methylene group contained in R ² may be substituted with a hetero atom. w represents an integer of 0 to 8.
R ^{3 to} R ¹¹ each independently represent an 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 aliphatic hydrocarbon group, aryl group and 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. ]   A silicon-containing acrylic resin (A) polymerizes at least a non-hydrolyzable polymerizable unsaturated compound (A1) having a silicon atom and an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (A2). The photosensitive resin composition according to claim 3 or 4, which is a silicon-containing acrylic resin containing a copolymer.   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). 6. The photosensitive resin composition according to claim 5, which is a silicon-containing acrylic resin. The photosensitive resin composition according to any one of claims 1 to 6, wherein the siloxane compound (B) (excluding (A)) is a compound containing a structural unit derived from the monomer represented by the formula (II). .

[In the formula (II), R ¹² and R ¹³ each independently represent an 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 includes a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, an amino group, a mercapto group, and an imino group. , An epoxy group or a (meth) acryloyl 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 in any one of Claims 1-7 containing a solvent (D).   The display element containing the pattern formed using the photosensitive resin composition in any one of Claims 1-8.