JP2008102351A - Positive photosensitive composition - Google Patents

Abstract

There is a need for a photosensitive composition for a protective film that can form a pattern by alkali development and has good heat resistance and foreign material characteristics.
A compound (A2) having a structural unit synthesized using at least a compound (a1) having two or more acid anhydride groups, a diamine (a2), and a polyvalent hydroxy compound (a3), and A positive photosensitive composition containing a 1,2-quinonediazide compound.
[Selection figure] None

Description

  The present invention relates to a positive photosensitive composition for producing a liquid crystal display element, an EL display element, and the like, a protective film or an insulating film produced from the composition, and a display element including the protective film or the insulating film.

  Patterned transparent films are used in many parts of liquid crystal display elements such as spacers, insulating films and protective films. In recent years, the performance of liquid crystal display elements represented by the VA mode and the IPS mode has increased, and the number of liquid crystal display elements having a protective film on a color filter has increased.

  For such a protective film, a thermosetting material or a photosensitive material is used, but when forming a protective film only on a necessary part or when forming a hole pattern in an insulating film, the photosensitive material is used. Is often used.

In addition, since the composition for the protective film and the composition for the insulating film are applied to the entire surface of the display element, there is a problem that a spec-out product is likely to occur due to a drop of a gel-like material attached to the coating nozzle. . In order to prevent this, “foreign matter characteristics” that are difficult to see even when foreign matter is present are important. “Foreign material characteristics” means that when a resin composition is applied and dried on a substrate on which foreign material exists, the film thickness around the foreign material is disturbed, resulting in disturbed reflected light around the foreign material. This is a phenomenon in which a foreign object is easily noticeable when viewed in a shape enlarged from the size of. “Excellent foreign material properties” means that such a phenomenon is unlikely to occur and foreign materials are not conspicuous. The foreign matter characteristics greatly affect the yield at the time of manufacturing the color film.
Japanese Patent Laid-Open No. 2005-105264 (Patent Document 1) describes a material having excellent foreign matter characteristics as a thermosetting protective film material, but the foreign matter characteristics so far for photosensitive protective film materials. For example, in a negative photosensitive composition of a type in which a polymerizable monomer is polymerized with a photopolymerization initiator, foreign material characteristics are deteriorated due to the influence of the polymerizable monomer contained (for example, JP, 2005-308874, A (patent documents 2)). On the other hand, a protective film and an insulating film using a positive photosensitive composition have also been proposed, but they have relatively excellent foreign material properties, but they are acrylic and have low heat resistance, and are also important as protective films. The flatness which is a characteristic is insufficient (Japanese Patent Laid-Open No. 5-165214 (Patent Document 3), Japanese Patent Laid-Open No. 2001-330953 (Patent Document 4), Japanese Patent Laid-Open No. 2002-287351 (Patent Document 5). ).
JP 2005-105264 A JP 2005-308874 A JP-A-5-165214 JP 2001-330953 A JP 2002-287351 A

  There is a need for a photosensitive composition for a protective film that can form a pattern by alkali development and has good heat resistance and foreign material characteristics.

  The inventors have a compound (A1) having a structural unit represented by the following formula (2) or a compound (A2) having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). And a positive photosensitive composition containing a 1,2-quinonediazide compound, and the present invention was completed based on this finding.

（式中、Ｒ¹とＲ³はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位を有する化合物（Ａ１）、および、１，２−キノンジアジド化合物を含有するポジ型感光性組成物。
［２］ 化合物（Ａ１）が、少なくとも、酸無水物基を２つ以上有する化合物（ａ１）と多価ヒドロキシ化合物（ａ３）とを用いて合成される、［１］に記載のポジ型感光性組成物。
［３］ 酸無水物基を２つ以上有する化合物（ａ１）が、テトラカルボン酸二無水物、および、酸無水物基を有する重合性モノマーと他の重合性モノマーとの共重合体からなる群から選ばれる１以上であり、
多価ヒドロキシ化合物（ａ３）がジオールである、［２］に記載のポジ型感光性組成物。
［４］ 化合物（Ａ１）が、
ジオール、テトラカルボン酸二無水物およびスチレン−無水マレイン酸共重合体の反応生成物、
ジオールおよびテトラカルボン酸二無水物の反応生成物、または、
ジオールおよびスチレン−無水マレイン酸共重合体の反応生成物
である、［１］に記載のポジ型感光性組成物。
［５］ 化合物（Ａ１）が、
ジオール、テトラカルボン酸二無水物、スチレン−無水マレイン酸共重合体および１価アルコールの反応生成物、
ジオール、テトラカルボン酸二無水物、スチレン−無水マレイン酸共重合体およびモノアミンの反応生成物、
ジオール、テトラカルボン酸二無水物および１価アルコールの反応生成物、
ジオール、テトラカルボン酸二無水物およびモノアミンの反応生成物、
ジオール、スチレン−無水マレイン酸共重合体および１価アルコールの反応生成物、または、
ジオール、スチレン−無水マレイン酸共重合体およびモノアミンの反応生成物
である、［１］に記載のポジ型感光性組成物。 [1] The following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A positive photosensitive composition containing a compound (A1) having a structural unit represented by formula (1) and a 1,2-quinonediazide compound.
[2] The positive photosensitive property according to [1], wherein the compound (A1) is synthesized using at least the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3). Composition.
[3] The compound (a1) having two or more acid anhydride groups is composed of tetracarboxylic dianhydride and a copolymer of a polymerizable monomer having an acid anhydride group and another polymerizable monomer. 1 or more selected from
The positive photosensitive composition as described in [2], wherein the polyvalent hydroxy compound (a3) is a diol.
[4] Compound (A1) is
Reaction product of diol, tetracarboxylic dianhydride and styrene-maleic anhydride copolymer,
Reaction product of diol and tetracarboxylic dianhydride, or
The positive photosensitive composition according to [1], which is a reaction product of a diol and a styrene-maleic anhydride copolymer.
[5] Compound (A1) is
Reaction product of diol, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monohydric alcohol,
Reaction product of diol, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monoamine,
Reaction product of diol, tetracarboxylic dianhydride and monohydric alcohol,
Reaction products of diols, tetracarboxylic dianhydrides and monoamines,
Reaction product of diol, styrene-maleic anhydride copolymer and monohydric alcohol, or
The positive photosensitive composition according to [1], which is a reaction product of a diol, a styrene-maleic anhydride copolymer and a monoamine.

（式中、Ｒ¹とＲ²はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位と、下記式（２）

（式中、Ｒ¹とＲ³はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位とを有する化合物（Ａ２）、および、１，２−キノンジアジド化合物を含有するポジ型感光性組成物。 [6] The diol is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. One or more selected,
Tetracarboxylic dianhydride is pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride One or more selected from the group consisting of things,
Monohydric alcohols are benzyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, propylene glycol monoethyl ether, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxy One or more selected from the group consisting of methyl oxetane,
Monoamine is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxy Silane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxy The positive photosensitive composition according to [4] or [5], which is one or more selected from the group consisting of silane, m-aminophenylmethyldiethoxysilane, and aminobenzoic acid.
[7] The following formula (1)

(In the formula, R ¹ and R ² are each independently an organic group having 2 to 100 carbon atoms.)
And the following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A positive photosensitive composition containing a compound (A2) having a structural unit represented by formula (1) and a 1,2-quinonediazide compound.

[8] The compound (A2) is synthesized using at least the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3). A positive photosensitive composition.
[9] The group in which the compound (a1) having two or more acid anhydride groups comprises a tetracarboxylic dianhydride and a copolymer of a polymerizable monomer having an acid anhydride group and another polymerizable monomer. 1 or more selected from
The positive photosensitive composition as described in [8], wherein the polyvalent hydroxy compound (a3) is a diol.
[10] Compound (A2) is
Reaction product of diol, diamine, tetracarboxylic dianhydride and styrene-maleic anhydride copolymer,
Reaction product of diol, diamine and tetracarboxylic dianhydride, or
Reaction product of diol, diamine and styrene-maleic anhydride copolymer,
The positive photosensitive composition as described in [7].
[11] Compound (A2) is
Reaction product of diol, diamine, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monohydric alcohol,
Reaction products of diols, diamines, tetracarboxylic dianhydrides, styrene-maleic anhydride copolymers and monoamines,
Reaction product of diol, diamine, tetracarboxylic dianhydride and monohydric alcohol,
Reaction products of diols, diamines, tetracarboxylic dianhydrides and monoamines,
Reaction product of diol, diamine, styrene-maleic anhydride copolymer and monohydric alcohol, or
Diol, diamine, styrene-maleic anhydride copolymer, monoamine reaction product,
The positive photosensitive composition as described in [7].

（式中、Ｒ⁴およびＲ⁵は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｒ⁶独立してはメチレン、フェニレンまたはアルキル置換されたフェニレンである。ｘは独立して１〜６の整数であり、ｙは１〜１０の整数である。）
で表される化合物なる群からから選ばれる１つ以上であり、
テトラカルボン酸二無水物が、ピロメリット酸二無水物、シクロブタンテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、１,２,４,５−シクロヘキサンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物および３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物からなる群から選ばれる１つ以上であり、
１価アルコールが、ベンジルアルコール、２−ヒドロキシエチルメタクリレート、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルおよび３−エチル−３−ヒドロキシメチルオキセタンからなる群から選ばれる１つ以上であり、
モノアミンが、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−アミノプロピルメチルジメトキシシラン、３−アミノプロピルメチルジエトキシシラン、および４−アミノ安息香酸からなる群から選ばれる１つ以上である、［１０］または［１１］に記載のポジ型感光性組成物。
［１３］ ジオールが、１，４−ブタンジオールであり、
ジアミンが、４，４'−ジアミノジフェニルスルホン、３，３'−ジアミノジフェニルスルホン、および下記式（Ａ）

（式中、Ｒ⁴およびＲ⁵は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｒ⁶独立してはメチレン、フェニレンまたはアルキル置換されたフェニレンである。ｘは独立して１〜６の整数であり、ｙは１〜１０の整数である。）
で表される化合物からなる群から選ばれる１つ以上であり、
テトラカルボン酸二無水物が、ピロメリット酸二無水物、ブタンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物および３，３’，４，４’−ジフェニルエーテルテトラカルボン酸二無水物からなる群から選ばれる１つ以上であり、
１価アルコールが、ベンジルアルコール、２−ヒドロキシエチルメタクリレート、ジエチレングリコールモノエチルエーテルおよび３−エチル−３−ヒドロキシメチルオキセタンからなる群から選ばれる１つ以上であり、
モノアミンが、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、ｐ−アミノフェニルトリメトキシシランおよびアミノ安息香酸からなる群から選ばれる１つ以上である、［１０］または［１１］に記載のポジ型感光性組成物。 [12] The diol is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. One or more selected,
Diamine is 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3 ′. -Dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-diaminodiphenylpropane, bis [4- (4-aminobenzyl) Phenyl] methane and the following formula (A)

Wherein R ⁴ and R ⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ^{6 is} independently methylene, phenylene or alkyl-substituted phenylene. X is independently 1 to 1 6 is an integer, and y is an integer of 1 to 10.)
One or more selected from the group consisting of compounds represented by:
Tetracarboxylic dianhydride is pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride One or more selected from the group consisting of things,
The monohydric alcohol is one or more selected from the group consisting of benzyl alcohol, 2-hydroxyethyl methacrylate, propylene glycol monoethyl ether, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane;
One selected from the group consisting of monoamino, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobenzoic acid; The positive photosensitive composition as described in [10] or [11].
[13] The diol is 1,4-butanediol,
Diamine is 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, and the following formula (A)

Wherein R ⁴ and R ⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ^{6 is} independently methylene, phenylene or alkyl-substituted phenylene. X is independently 1 to 1 6 is an integer, and y is an integer of 1 to 10.)
One or more selected from the group consisting of compounds represented by:
Tetracarboxylic dianhydrides are pyromellitic dianhydride, butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4. One or more selected from the group consisting of '-diphenyl ether tetracarboxylic dianhydride,
The monohydric alcohol is one or more selected from the group consisting of benzyl alcohol, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane;
[10] or [11], wherein the monoamine is one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane, and aminobenzoic acid. The positive photosensitive composition as described.

（式中、Ｒ¹とＲ³はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位を有する化合物（Ａ１）、ならびに、
１，２−キノンジアジド化合物を含有するポジ型感光性組成物。
［１５］ テトラカルボン酸二無水物およびスチレン−無水マレイン酸共重合体の反応生成物からなる群から選ばれる１つ以上である酸無水物基を２つ以上有する化合物（ａ１）と、４，４'−ジアミノジフェニルスルホン、３，３'−ジアミノジフェニルスルホン、３，４'−ジアミノジフェニルスルホン、４，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルメタン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２’−ジアミノジフェニルプロパンおよびビス［４−（４−アミノベンジル）フェニル］メタンからなる群から選ばれる１つ以上であるジアミン（ａ２）と、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオールおよび１，８−オクタンジオールからなる群から選ばれる１つ以上である多価ヒドロキシ化合物（ａ３）と、を用いて合成される 下記式（１）

（式中、Ｒ¹とＲ²はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位と、下記式（２）

（式中、Ｒ¹とＲ³はそれぞれ独立して炭素数２〜１００の有機基である。）
で示される構成単位とを有する化合物（Ａ２）、ならびに、
１，２−キノンジアジド化合物を含有するポジ型感光性組成物。 [14] Compound (a1) having two or more acid anhydride groups which are one or more selected from the group consisting of a reaction product of tetracarboxylic dianhydride and styrene-maleic anhydride copolymer, ethylene glycol And one or more selected from the group consisting of propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol A hydroxy compound (a3) and the following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A compound (A1) having a structural unit represented by:
A positive photosensitive composition containing a 1,2-quinonediazide compound.
[15] Compound (a1) having two or more acid anhydride groups that are one or more selected from the group consisting of a reaction product of tetracarboxylic dianhydride and styrene-maleic anhydride copolymer; 4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4, Consists of 4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2′-diaminodiphenylpropane and bis [4- (4-aminobenzyl) phenyl] methane Diamine (a2) which is one or more selected from the group, ethylene glycol, propylene glycol, 1,4- A polyvalent hydroxy compound (a3) which is one or more selected from the group consisting of tandiol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol, The following formula (1)

(In the formula, R ¹ and R ² are each independently an organic group having 2 to 100 carbon atoms.)
And the following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A compound (A2) having a structural unit represented by:
A positive photosensitive composition containing a 1,2-quinonediazide compound.

[16] 1,2-quinonediazide compound is 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid Ester, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester The positive photosensitive composition according to any one of [1] to [15], which is one or more selected from the group.
[17] 1,2-quinonediazide compound is 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonic acid ester and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5 The positive photosensitive composition according to [1] to [15], which is one or more selected from the group consisting of sulfonate esters.

（式中、ｎは０〜１０の整数である。）
［２０］ エポキシ樹脂（Ｃ）が、オキシランを有するモノマーの重合体、および、オキシランを有するモノマーと他のモノマーとの共重合体からなる群から選ばれる１つ以上である、［１８］に記載のポジ型感光性組成物。
［２１］ オキシランを有するモノマーが、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレートから選ばれる１つ以上である、［１８］に記載のポジ型感光性組成物。
［２２］ ［１］〜［２１］のいずれか１項に記載のポジ型感光性組成物の透明膜またはパターン状透明膜。 [18] The positive photosensitive composition according to any one of [1] to [17], further comprising an epoxy resin (C).
[19] The positive photosensitive composition according to [17], wherein the epoxy resin (C) is one or more selected from compounds represented by the following formulas (C1) to (C4).

(In the formula, n is an integer of 0 to 10.)
[20] The epoxy resin (C) is at least one selected from the group consisting of a polymer of a monomer having an oxirane and a copolymer of a monomer having an oxirane and another monomer. A positive photosensitive composition.
[21] The positive photosensitive resin according to [18], wherein the monomer having oxirane is one or more selected from glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. Sex composition.
[22] A transparent film or a patterned transparent film of the positive photosensitive composition according to any one of [1] to [21].

  In this specification, in order to show both acrylic acid and methacrylic acid, it may describe as "(meth) acrylic acid". Similarly, in order to indicate both acrylate and methacrylate, it may be expressed as “(meth) acrylate”.

The positive photosensitive composition according to a preferred embodiment of the present invention is excellent in heat resistance, flatness, foreign matter characteristics and the like. When the positive photosensitive composition according to a preferred embodiment of the present invention is used, a pattern can be formed by alkali development which is excellent in heat resistance, flatness, foreign matter characteristics and the like.
In addition, the pattern-like transparent film of the positive photosensitive composition according to a preferred embodiment of the present invention can be used as a color filter protective film for a liquid crystal display element or an insulating film for a TFT substrate, thereby contributing to an improvement in yield. it can.

1 Positive Photosensitive Composition of the Present Invention A first aspect of the present invention is a positive photosensitive composition containing a compound (A1) having a structural unit represented by the above formula (2) and a 1,2-quinonediazide compound. Relates to the composition.
Moreover, the 1st aspect of this invention contains the compound (A2) which has a structural unit shown by the said Formula (1), and the structural unit shown by the said Formula (2), and a 1, 2- quinonediazide compound. The present invention relates to a positive photosensitive composition.
These positive photosensitive compositions can be obtained by mixing the compound (A1) or the compound (A2) and a 1,2-quinonediazide compound. The composition is further optionally mixed with an epoxy resin or a solvent, and depending on the desired properties, various additives such as coupling agents and surfactants, polyvalent carboxylic acids and the like are selected as necessary. And then uniformly mixing and dissolving them.

1.1 Compound (A1)
1.1.1 Structural Unit Included in Compound (A1) The compound (A1) contained in the positive photosensitive composition of the present invention contains, for example, a structural unit represented by the above formula (2).
In the above formula (2), R ¹ is an organic group having 2 to 100 carbon atoms, and this R ¹ is a residue of a compound having two or more acid anhydride groups, preferably tetracarboxylic dianhydride. Residue or styrene-maleic anhydride copolymer residue. In the above formula (2), R ³ is an organic group having 2 to 100 carbon atoms, and this R ³ is a polyvalent hydroxy compound residue, preferably a diol residue.

  The compound (A1) includes the above structural unit, and the terminal thereof is preferably composed of an acid anhydride group, amino, hydroxy and the like.

  The chemical resistance of the positive photosensitive composition of the present invention is preferably a high molecular weight, while the solubility in a solvent is preferably a low molecular weight. Therefore, the weight average molecular weight of the compound (A1) is 1, It is preferable that it is 000-200,000, and 2,000-150,000 are more preferable.

  In the present invention, the concentration of the compound (A1) in the positive photosensitive composition is not particularly limited, but is preferably 2 to 50% by weight. Within this concentration range, the viscosity of the positive photosensitive composition is preferable, and a coating film having a uniform film thickness can be formed by various coating methods.

  In the present invention, the compound (A1) may be used in a positive photosensitive composition after being partially or completely imidized by heating or dehydration treatment.

1.1.2 Production Method of Compound (A1) The compound (A1) contained in the positive photosensitive composition of the present invention is, for example, at least a compound (a1) having two or more acid anhydride groups and a polyvalent compound. It can be obtained by reacting with a hydroxy compound (a3).
The compound (A1) obtained by such a method preferably has the structural unit of the above formula (2), but is not limited to having the structural unit.

  Below, the compound (a1) and polyvalent hydroxy compound (a3) which have two or more acid anhydride groups which can be used in order to obtain a compound (A1) are demonstrated.

(1) Compound (a1) having two or more acid anhydride groups
Specific examples of the compound (a1) having two or more acid anhydride groups that can be used to obtain the compound (A1) include a styrene-maleic anhydride copolymer, styrene-maleic anhydride- (meth). Acrylic acid copolymer, (meth) acrylic acid methyl-maleic anhydride copolymer, (meth) methyl acrylate-maleic anhydride- (meth) acrylic acid copolymer, styrene-itaconic anhydride copolymer, styrene -Itaconic anhydride- (meth) acrylic acid copolymer, (meth) acrylic acid methyl-itaconic anhydride copolymer, (meth) acrylic acid methyl-itaconic anhydride- (meth) acrylic acid copolymer, 2, 2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfate Tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane Dianhydrides, and aromatic tetracarboxylic dianhydrides such as ethylene glycol bis (anhydro trimellitate) (trade name; TMEG-100, manufactured by Shin Nippon Rika Co., Ltd.), ethane tetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetra Dorofuriru) methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, and tetracarboxylic acid dianhydride, such as compounds represented by the following formula a1-1~a1-73 the like.

Among the above specific examples of the compound (a1) having two or more acid anhydride groups, styrene-maleic anhydride copolymer, styrene-maleic anhydride- (meth) acrylic acid copolymer, methyl (meth) acrylate -Maleic anhydride copolymer, pyromellitic dianhydride (a1-1), cyclobutanetetracarboxylic dianhydride (a1-14), butanetetracarboxylic dianhydride (a1-18), 1,2, 4,5-cyclohexanetetracarboxylic dianhydride (a1-20), 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (a1-8), 3,3 ′, 4,4 ′ -When the diphenyl ether tetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (a1-6) are used, the durability of the coating film of the resulting positive photosensitive composition But Preferably from Kunar.
Among these, styrene-maleic anhydride copolymer, pyromellitic dianhydride, butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and 3,3 Since the transparency of the coating film of the positive photosensitive composition obtained using ', 4,4'-diphenyl ether tetracarboxylic dianhydride is high, it is preferable.

In addition, the compound (a1) having an acid anhydride group that can be used for synthesizing the compound (A1) contained in the positive photosensitive composition of the present invention is not limited to the compound of the present specification. As long as the object of the present invention is achieved, other various compounds having acid anhydride groups can be used.
In addition, the compound (a1) having an acid anhydride group that can be used for synthesizing the compound (A1) contained in the positive photosensitive composition of the present invention is one kind alone, or two or more kinds. They can be used in combination. That is, as a combination of two or more, the compounds having the acid anhydride group, the compound having the acid anhydride group and the compound having the other acid anhydride group, or the compound having the acid anhydride group Compounds having an acid anhydride group other than the above can be used.

(2) Polyvalent hydroxy compound (a3)
As the polyvalent hydroxy compound (a3) that can be used for obtaining the compound (A1), a diol is preferable. Specific examples of the polyvalent hydroxy compound (a3) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Polypropylene glycol having a molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentanediol 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,7 -Heptane 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, bisphenol A (trade name), bisphenol S (trade name), bisphenol F (trade name), diethanolamine, and triethanolamine, SEO-2 (trade name, (Manufactured by Nikka Chemical Co., Ltd.), SKY CHDM, Ricabinol HB Co., Ltd.), SILAPLANE FM-4411 (manufactured by product name, Chisso Co., Ltd.), and the like.

  Among the above specific examples of the polyvalent hydroxy compound (a3), ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol is preferable, and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are preferable because transparency of the resulting positive photosensitive composition is increased.

In addition, the polyvalent hydroxy compound (a3) that can be used for synthesizing the compound (A1) contained in the positive photosensitive composition of the present invention is not limited to the polyvalent hydroxy compound of the present specification. Various other forms of polyvalent hydroxy compounds can be used as long as the object of the present invention is achieved.
Moreover, the polyvalent hydroxy compound (a3) that can be used for synthesizing the compound (A1) contained in the positive photosensitive composition of the present invention is used singly or in combination of two or more. Can do. That is, as the combination of two or more kinds, the above polyvalent hydroxy compounds, the above polyvalent hydroxy compounds and other polyvalent hydroxy compounds, or polyvalent hydroxy compounds other than the above polyvalent hydroxy compounds can be used. .

(3) Monohydric alcohol When the compound (A1) used in the present invention has an acid anhydride group at the molecular end, it is preferable to react by introducing a monohydric alcohol. Reaction with a monohydric alcohol simultaneously with the compound (a1) or polyvalent hydroxy compound (a3) having an acid anhydride group, or after the compound (a1) and polyvalent hydroxy compound (a3) having an acid anhydride group are added Put it into the system. The compound (A1) obtained by reacting with a monohydric alcohol is preferable because of good flatness.
Specific examples of the monohydric alcohol added include methanol, ethanol, 1-propanol, isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether. , Dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, linalool, terpineol, dimethylbenzyl carbinol, ethyl lactate, glycidol, 3- Ethyl-3-hydroxymethyl oxetane etc. It can gel.
Among these, isopropyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are preferable. When benzyl alcohol is used, a coating film of the obtained positive photosensitive composition can be obtained. It becomes flat and preferable.

(4) Other raw materials 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-amino Butyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-amino A silicon-containing monoamine such as phenyltrimethoxysilane or m-aminophenylmethyldiethoxysilane, or a carboxyl-containing monoamine such as 4-aminobenzoic acid is reacted with a compound (A1) having an acid anhydride group at the molecular end. If is preferred chemical resistance of the coating film of the positive photosensitive composition obtained is improved.
Further, the silicon-containing monoamine can be charged into the reaction system simultaneously with the monohydric alcohol to react with the compound (A1).

(5) Reaction conditions The compound (A1) has 0.5 to 1 hydroxy of the polyvalent hydroxy compound (a3) with respect to 1 mol of the acid anhydride of the compound (a1) having two or more acid anhydride groups. It is preferably obtained by reaction of 5 mol, more preferably obtained by reaction of 0.8 to 1.2 mol.

  The solvent used for the synthesis reaction of the compound (A1) is not particularly limited, but a solvent capable of dissolving the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3) is used. preferable.

  Specific examples of the reaction solvent for synthesizing the compound (A1) include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3- Mention may be made of methyl methoxypropionate, ethyl 3-ethoxypropionate, cyclohexanone, N-methyl-2-pyrrolidone and N, N-dimethylacetamide. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, diethylene glycol methyl ethyl ether, and N-methyl-2-pyrrolidone are preferable.

  These reaction solvents can be used alone or as a mixed solvent of two or more. Moreover, if it is a ratio of 50 weight% or less, in addition to the said reaction solvent, another solvent can also be mixed and used.

  When the reaction solvent is used in an amount of 100 parts by weight or more based on a total of 100 parts by weight of the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3), and optionally included monohydric alcohol, monoamine, etc. Since the synthesis reaction proceeds smoothly, it is preferable. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours. When the silicon-containing monoamine is reacted, after the reaction between the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3) is completed, the reaction solution is cooled to 40 ° C. or lower, Silicon-containing monoamine may be added and reacted at 10 to 40 ° C. for 0.1 to 6 hours. The monohydric alcohol is preferably added simultaneously with the polyvalent hydroxy compound.

(6) Order of charging into reaction system There is no particular limitation on the order of charging reaction raw materials into the reaction system. That is, the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3) are simultaneously added to the reaction solvent, and the compound (a1) having two or more acid anhydride groups is dissolved in the reaction solvent. Any method such as charging the polyvalent hydroxy compound (a3) after adding the compound, and charging the compound (a1) having two or more acid anhydride groups after dissolving the polyvalent hydroxy compound (a3) in the reaction solvent. Can also be used.

1.2 Compound (A2)
1.2.1 Constituent Units Contained in Compound (A2) The compound (A2) contained in the positive photosensitive composition of the present invention is, for example, a constituent unit represented by the above formula (1) and the above formula (2). And a structural unit represented by
In the above formula (1), R ¹ is an organic group having 2 to 100 carbon atoms, and this R ¹ is a residue of a compound having two or more acid anhydride groups, preferably tetracarboxylic dianhydride. Residue or styrene-maleic anhydride copolymer residue. In the above formula (2), R ² is an organic group having 2 to 100 carbon atoms, and preferably R ² is a diamine residue.

  The compound (A2) includes the above structural unit, and the terminal thereof is preferably composed of an acid anhydride group, amino, hydroxy and the like.

  The weight average molecular weight of the compound (A2) and the concentration of the compound (A2) in the positive photosensitive composition are the same as those of the compound (A1).

In the present invention, the compound (A2) may be used in a positive photosensitive composition after being partially or completely imidized by heating or dehydration treatment.
1.2.2 Production Method of Compound (A2) The compound (A2) contained in the positive photosensitive composition of the present invention includes, for example, at least a compound (a1) having two or more acid anhydride groups and a diamine ( It can be obtained by reacting a2) with a polyvalent hydroxy compound (a3).
Although it is preferable that the compound (A2) obtained by such a method has the structural unit of the said Formula (1) and the structural unit of the said Formula (2), it is not limited to having the said structural unit.

  Hereinafter, the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3) that can be used for obtaining the compound (A2) are used for obtaining the compound (A1). This is the same as the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3). Therefore, the diamine (a2) that can be used to obtain the compound (A2) will be described below.

(1) Diamine (a2)
In the present invention, the diamine (a2) used for the synthesis of the compound (A2) is not particularly limited as long as it has two amino groups. For example, the general formula NH ₂ —R—NH ₂ (wherein , R is an organic group having 2 to 100 carbon atoms). Specific examples of the compound represented by the general formula include compounds represented by the following general formulas (II) to (VIII).

［式（II）および（IV）中、
Ａ¹は、−（ＣＨ₂）_m−であり、ここでｍは１〜６の整数であり、
式（VI）〜（VIII）中、
Ａ¹は、単結合、−Ｏ−、−Ｓ−、−Ｓ−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−、−（ＣＨ₂）_m−、−Ｏ−（ＣＨ₂）_m−Ｏ−、−Ｓ−（ＣＨ₂）_m−Ｓ−であり、ここでｍは１〜６の整数であり、
Ａ²は、単結合、−Ｏ−、−Ｓ−、−ＣＯ−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＦ₃）₂−または炭素数１〜３のアルキレンであり、
シクロヘキサン環またはベンゼン環に結合している水素は、−Ｆ、−ＣＨ₃と置き換えられていてもよい。］

[In the formulas (II) and (IV),
A ¹ is — (CH ₂ ) _m —, where m is an integer of 1 to 6,
In formulas (VI) to (VIII),
A ¹ is a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —NHCO—, —C (CH ₃ ) ₂ —, —C ( CF ₃ ) ₂ —, — (CH ₂ ) _m —, —O— (CH ₂ ) _m —O—, and —S— (CH ₂ ) _m —S—, where m is an integer of 1-6. Yes,
A ² is a single bond, —O—, —S—, —CO—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ — or alkylene having 1 to 3 carbon atoms,
Hydrogen bonded to a cyclohexane ring or a benzene ring may be replaced with -F or -CH ₃ . ]

  Examples of the diamine represented by the general formula (II) include diamines represented by the formulas (II-1) to (II-3).

Examples of the diamine represented by the general formula (III) include diamines represented by the formulas (III-1) and (III-2).

Examples of the diamine represented by the general formula (IV) include diamines represented by the formulas (IV-1) to (IV-3).

Examples of the diamine represented by the general formula (V) include diamines represented by the formulas (V-1) to (V-5).

Examples of the diamine represented by the general formula (VI) include diamines represented by the formulas (VI-1) to (VI-30).

Examples of the diamine represented by the general formula (VII) include diamines represented by the formulas (VII-1) to (VII-6).

Examples of the diamine represented by the general formula (VIII) include diamines represented by the formulas (VIII-1) to (VIII-11).

  Among the specific examples of the diamine (a2) represented by the general formulas (II) to (VIII), more preferably, the formulas (V-1) to (V-5) and the formulas (VI-1) to (VI) -12), formula (VI-26), formula (VI-27), formula (VII-1), formula (VII-2), formula (VII-6), formula (VIII-1) to (VIII-5) Diamines represented by formula (V-6), formula (V-7), and diamines represented by formulas (VI-1) to (VI-12).

［式（IX）中、
Ａ³は、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯ−、−ＣＯＮＨ−または−（ＣＨ₂）_m−（式中、ｍは１〜６の整数である）であり、
Ｒ⁶は、炭素数１〜３０の有機基であり、該有機基の末端は−Ｈまたはハロゲンであってもよく、好ましくは、該有機基はステロイド骨格を有する基、下記式（Ｘ）で表される基、または、ベンゼン環に結合している２つのアミノの位置関係がパラ位のときは炭素数１〜２０のアルキル、もしくは該位置関係がメタのときは炭素数１〜１０のアルキルまたはフェニルであり、
該アルキルにおいては、任意の−ＣＨ₂−が−ＣＦ₂−、−ＣＨＦ−、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられていてもよく、−ＣＨ₃が−ＣＨ₂Ｆ、−ＣＨＦ₂または−ＣＦ₃で置き換えられていてもよく
該フェニルの環形成炭素に結合している水素は、−Ｆ、−ＣＨ₃、−ＯＣＨ₃、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂または−ＯＣＦ₃と置き換えられていてもよい。］

［式（X）中、
Ａ⁴およびＡ⁵はそれぞれ独立して、単結合、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＮＨ−、−ＣＨ＝ＣＨ−または炭素数１〜１２のアルキレンであり、
Ｒ⁷およびＲ⁸はそれぞれ独立して、−Ｆまたは−ＣＨ₃であり、
環Ｓは１，４−フェニレン、１，４−シクロヘキシレン、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，７−ジイルまたはアントラセン−９，１０−ジイルであり、
Ｒ⁹は−Ｈ、−Ｆ、炭素数１〜１２のアルキル、炭素数１〜１２のフッ素置換アルキル、炭素数１〜１２のアルコキシ、−ＣＮ、−ＯＣＨ₂Ｆ、−ＯＣＨＦ₂または−ＯＣＦ₃であり、
ａおよびｂはそれぞれ独立して０〜４の整数を表し、
ｃ、ｄおよびｅはそれぞれ独立して０〜３の整数を表し、ｅが２または３であるとき複数の環Ｓは同一の基であっても異なる基であってもよく、
ｆおよびｇはそれぞれ独立して０〜２の整数を表し、かつ
ｃ＋ｄ＋ｅ≧１である。］ In the present invention, examples of the diamine (a2) used for the synthesis of the compound (A2) further include a diamine represented by the general formula (IX).

[In the formula (IX),
A ³ is a single bond, —O—, —COO—, —OCO—, —CO—, —CONH— or — (CH ₂ ) _m — (wherein m is an integer of 1 to 6). ,
R ⁶ is an organic group having 1 to 30 carbon atoms, and the terminal of the organic group may be —H or halogen. Preferably, the organic group is a group having a steroid skeleton, represented by the following formula (X): Or a C 1-10 alkyl when the position of the two amino groups bonded to the benzene ring is para, or a C 1-10 alkyl when the position is meta. Or phenyl,
In the alkyl, any —CH ₂ — may be replaced by —CF ₂ —, —CHF—, —O—, —CH═CH— or —C≡C—, and —CH ₃ may be —CH ₂ F, —CHF ₂ or —CF ₃ may be replaced. The hydrogen bonded to the ring-forming carbon of the phenyl is —F, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF _2. Alternatively, it may be replaced with —OCF ₃ . ]

[In the formula (X),
A ⁴ and A ⁵ are each independently a single bond, —O—, —COO—, —OCO—, —CONH—, —CH═CH—, or alkylene having 1 to 12 carbons,
R ⁷ and R ⁸ are each independently —F or —CH ₃ ;
Ring S is 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- Diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl;
R ⁹ is —H, —F, alkyl having 1 to 12 carbons, fluorine-substituted alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF _3. And
a and b each independently represents an integer of 0 to 4;
c, d and e each independently represent an integer of 0 to 3, and when e is 2 or 3, the plurality of rings S may be the same group or different groups,
f and g each independently represent an integer of 0 to 2 and c + d + e ≧ 1. ]

In the general formula (IX), two aminos are bonded to the phenyl ring carbon. Preferably, the bonding position of the two aminos is preferably the meta position or the para position. Further, the two amino groups are preferably bonded to the 3rd and 5th positions or the 2nd and 5th positions, respectively, when the bonding position of “R ⁶ —A ³ —” is the 1st position.
Examples of the diamine represented by the general formula (IX) include diamines represented by the following formulas (IX-1) to (IX-11).

In the above formulas (IX-1), (IX-2), (IX-7) and (IX-8), R ¹⁸ is alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. Among these, alkyl having 5 to 12 carbons or alkoxy having 5 to 12 carbons is preferable. In the formulas (IX-3) to (IX-6) and (IX-9) to (IX-11), R ¹⁹ is alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons. Of these, alkyl having 3 to 10 carbon atoms or alkoxy having 3 to 10 carbon atoms is preferable.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-12) to (IX-17).

In the above formulas (IX-12) to (IX-15), R ²⁰ is alkyl having 4 to 16 carbons, preferably alkyl having 6 to 16 carbons. In the formula (IX-16) and the formula (IX-17), R ²¹ is alkyl having 6 to 20 carbon atoms, preferably alkyl having 8 to 20 carbon atoms.

  Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-18) to (IX-38).

The above formulas (IX-18), (IX-19), (IX-22), (IX-24), (IX-25), (IX-28), (IX-30), (IX-31), In (IX-36) and (IX-37), R ²² is alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons, preferably alkyl having 3 to 12 carbons or alkoxy having 3 to 12 carbons. . In addition, the above formulas (IX-20), (IX-21), (IX-23), (IX-26), (IX-27), (IX-29), (IX-32) to (IX-35) ) And (IX-38), R ²³ is —H, —F, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, —CN, —OCH ₂ F, —OCHF ₂ or —OCF ₃ . Yes, C3-C12 alkyl or C3-C12 alkoxy is more preferable. In the above formulas (IX-33) and (IX-34), A ₉ is alkylene having 1 to 12 carbons.

Examples of the diamine represented by the general formula (IX) further include diamines represented by the following formulas (IX-39) to (IX-48).

  Of the diamines (a2) represented by the general formula (IX), diamines represented by the formulas (IX-1) to (IX-11) are preferable, and the formulas (IX-2) and (IX-4) are preferred. More preferred are diamines represented by formula (IX-5) and formula (IX-6).

［式（XI）と（XII）中、
Ｒ¹⁰は−Ｈまたは−ＣＨ₃であり、
Ｒ¹¹はそれぞれ独立して、−Ｈまたは炭素数１〜２０のアルキルもしくは炭素数２〜２０のアルケニルであり、
Ａ⁶はそれぞれ独立して、単結合、−Ｃ（＝Ｏ）−または−ＣＨ₂−であり、
Ｒ¹³およびＲ¹⁴はそれぞれ独立して、−Ｈ、炭素数１〜２０のアルキルまたはフェニルである。］ In the present invention, examples of the diamine (a2) used for the synthesis of the compound (A2) further include compounds represented by the following general formulas (XI) and (XII).

[In the formulas (XI) and (XII)
R ¹⁰ is —H or —CH ₃ ;
Each R ¹¹ is independently —H or alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
Each A ⁶ is independently a single bond, —C (═O) — or —CH ₂ —;
R ¹³ and R ¹⁴ are each independently —H, C 1-20 alkyl or phenyl. ]

In the general formula (XI), it is preferable that one of the two “NH ₂ —Ph—A ₆ —O—” is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position. The two amino groups are each bonded to a phenyl ring carbon, and preferably bonded to the meta position or the para position with respect to the bonding position of A ⁶ .
Examples of the diamine represented by the general formula (XI) include diamines represented by the formulas (XI-1) to (XI-4).

In the general formula (XII), two “NH ₂ — (R ₁₄ —) Ph—A ⁶ —O—” are each bonded to the phenyl ring carbon, but preferably to the carbon to which the steroid nucleus is bonded. On the other hand, it is bonded to carbon in the meta or para position. The two aminos are each bonded to the phenyl ring carbon, but are preferably bonded to the meta or para position with respect to A ⁶ .
Examples of the diamine represented by the general formula (XII) include diamines represented by the formulas (XII-1) to (XII-8).

［式（XIII）中、Ｒ¹⁵は−Ｈまたは炭素数１〜２０のアルキルであり、該アルキルのうち炭素数２〜２０のアルキルの任意の−ＣＨ₂−は、−Ｏ−、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、
Ａ⁷はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンであり、
Ａ⁸は単結合または炭素数１〜３のアルキレンであり、
環Ｔは１，４−フェニレンまたは１，４−シクロヘキシレンであり、
ｈは０または１である。］

［式（XIV）中、
Ｒ¹⁶は炭素数２〜３０のアルキルであり、
Ｒ¹⁷は−Ｈまたは炭素数１〜３０のアルキルであり、
Ａ⁷はそれぞれ独立して−Ｏ−または炭素数１〜６のアルキレンである。］ In the present invention, examples of the diamine (a2) used for the synthesis of the compound (A2) further include compounds represented by general formulas (XIII) and (XIV).

[In the formula (XIII), R ¹⁵ is —H or alkyl having 1 to 20 carbons, and of the alkyls, any —CH ₂ — in the alkyl having 2 to 20 carbons is —O—, —CH═. CH— or —C≡C— may be substituted,
Each A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms;
A ⁸ is a single bond or alkylene having 1 to 3 carbon atoms,
Ring T is 1,4-phenylene or 1,4-cyclohexylene,
h is 0 or 1. ]

[In the formula (XIV),
R ¹⁶ is alkyl having 2 to 30 carbons,
R ¹⁷ is —H or alkyl having 1 to 30 carbons;
A ⁷ is independently —O— or alkylene having 1 to 6 carbon atoms. ]

上記式（XIII-１）〜（XIII-３）において、Ｒ²⁴は炭素数−Ｈ、１〜２０のアルキルが好ましく、（XIII-４）〜（XIII-９）においてＲ²⁵は−Ｈ、炭素数１〜１０のアルキルがさらに好ましい。 In the general formula (XIII), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or para to A ⁷ .
Examples of the diamine represented by the general formula (XIII) include diamines represented by the formulas (XIII-1) to (XIII-9).

In the above formulas (XIII-1) to (XIII-3), R ²⁴ is preferably —H, alkyl having 1 to 20 carbons, and in (XIII-4) to (XIII-9), R ²⁵ is —H, carbon. The alkyl having 1 to 10 is more preferable.

In the general formula (XIV), the two amino groups are each bonded to the phenyl ring carbon, but are preferably bonded to the meta position or the para position with respect to A ⁷ .
Examples of the diamine represented by the general formula (XIV) include diamines represented by (XIV-1) to (XIV-3).

In the formulas (XIV-1) to (XIV-3), R ²⁶ is alkyl having 2 to 30 carbons, and among these, alkyl having 6 to 20 carbons is preferable, and R ²⁷ is —H or carbon number 1 to 1. 30 alkyl, and among these, -H or alkyl having 1 to 10 carbon atoms is more preferable.

  As described above, in the present invention, as the diamine (a2) used for the synthesis of the compound (A2), for example, diamines represented by the general formulas (I) to (XIV) can be used. The diamine can also be used. For example, a naphthalene diamine having a naphthalene structure, a fluorene diamine having a fluorene structure, a siloxane diamine having a siloxane bond, or the like can be used alone or mixed with another diamine.

（式中、Ｒ⁴およびＲ⁵は独立して炭素数１〜３のアルキルまたはフェニルであり、Ｒ⁶は独立してはメチレン、フェニレンまたはアルキル置換されたフェニレンであり、ｘは独立して１〜６の整数であり、ｙは１〜７０の整数である。ここで、より好ましいｙは１〜１５の整数である。）
ここで、「アルキル置換されたフェニレン」における、「アルキル」は、炭素数２〜１０のアルキルであることが好ましく、炭素数２〜６のアルキルであることが更に好ましい。アルキルの例としては、制限するわけではないが、エチル、プロピル、イソプロピル、ブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、ドデカニル等を挙げることができる。 The siloxane-based diamine is not particularly limited, but those represented by the following formula (A) can be preferably used in the present invention.

Wherein R ⁴ and R ⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ⁶ is independently methylene, phenylene or alkyl-substituted phenylene, and x is independently 1 And y is an integer of 1 to 70. Here, more preferable y is an integer of 1 to 15.)
Here, “alkyl” in “alkyl-substituted phenylene” is preferably alkyl having 2 to 10 carbon atoms, more preferably alkyl having 2 to 6 carbon atoms. Examples of alkyl include, but are not limited to, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, pentyl, hexyl, dodecanyl and the like.

Among these, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 2,2'- Diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-Aminobenzyl) phenyl] methane, 1,1-bis [4- (4-aminobenzyl) pheny ] Cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] methane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone , [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- 3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, a compound represented by the above formula A, etc. When used, it is preferable because the durability of the coating film of the obtained positive photosensitive composition is increased.
Among these, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′- Positive photosensitive composition obtained by using diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and 2,2′-diaminodiphenylpropane and the compound represented by the above formula A Since the transparency of the coating film of a thing is high, it is preferable.

The diamine (a2) that can be used to synthesize the compound (A2) contained in the positive photosensitive composition of the present invention is not limited to the diamine of the present specification, and the object of the present invention is Various other forms of diamine can be used as long as they are achieved.
Moreover, the diamine (a2) which can be used in order to synthesize | combine the compound (A2) contained in the positive photosensitive composition of this invention can be used individually by 1 type or in combination of 2 or more types. That is, as a combination of two or more kinds, the diamines described above, the diamine and other diamines, or diamines other than the diamines can be used.

(2) Monohydric alcohol When the compound (A2) used in the present invention has an acid anhydride group at the molecular end, it is preferable to react by adding a monohydric alcohol. The monohydric alcohol that can be used is the same as the monohydric alcohol used for the synthesis of the compound (A1).

(3) Other raw materials Similarly to the compound (A1), a compound (A2) having an acid anhydride group at the molecular end of a silicon-containing monoamine including the specific examples described above or a carboxyl-containing monoamine such as 4-aminobenzoic acid. And the chemical resistance of the coating film of the resulting positive photosensitive composition is improved.

(4) Reaction conditions Compound (A2) is an acid anhydride of compound (a1) having two or more acid anhydride groups, and the amount of amino of diamine (a2) is 0.1 to 0.9 mol. The polyhydroxy compound (a3) is preferably obtained by reacting 0.1 to 0.9 mol of hydroxy. In addition, compound (A2) is a compound having a polyhydric acid content of 0.2 to 0.8 mol of diamine (a2) with respect to 1 mol of acid anhydride of compound (a1) having two or more acid anhydride groups. More preferably, the hydroxy of the hydroxy compound (a3) is obtained by reacting 0.2 to 0.8 mol of hydroxy.

  The solvent used in the reaction is not particularly limited, but a solvent capable of dissolving the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3). preferable.

  The reaction solvent for synthesizing the compound (A2) is the same as the reaction solvent for synthesizing the compound (A1).

  The reaction solvent is used with respect to a total of 100 parts by weight of the compound (a1), the diamine (a2), the polyvalent hydroxy compound (a3) having two or more acid anhydride groups, and a monohydric alcohol, monoamine and the like optionally contained. Use of 100 parts by weight or more is preferable because the synthesis reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours. In the case of reacting a silicon-containing monoamine, after the reaction of the compound (a1) having two or more acid anhydride groups, the diamine (a2) and the polyvalent hydroxy compound (a3) is completed, the reaction solution is kept at 40 ° C. or lower. After cooling to 10 minutes, silicon-containing monoamine may be added and reacted at 10 to 40 ° C. for 0.1 to 6 hours. The monohydric alcohol is preferably added simultaneously with the polyvalent hydroxy compound.

(5) Order of charging into reaction system Similar to the synthesis of compound (A1), the order of charging the reaction raw materials into the reaction system in the synthesis of compound (A2) is not particularly limited.

1.3 1,2-quinonediazide compound Examples of the compound used as the 1,2-quinonediazide compound contained in the positive photosensitive composition of the present invention include 1,2-benzoquinonediazidesulfonic acid ester, 1,2- Naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonamide, 1,2-naphthoquinone diazide sulfonamide, and the like. These may be used alone or in combination of two or more.

Specific examples of 1,2-benzoquinonediazide sulfonic acid ester include 2,3,4-trihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1, 2-benzoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-benzoquinonediazide -5-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1, 2-benzoquinonediazide-5-sulfonic acid ester, 2,3,3 ′ 4-tetrahydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-benzoquinonediazide-5-sulfonic acid ester, 2,3,4 , 4′-tetrahydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-benzoquinonediazide-5-sulfonic acid ester, bis (2 , 4-Dihydroxyphenyl) methane-1,2-benzoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-benzoquinonediazide-5-sulfonic acid ester, bis (p-hydroxy) Phenyl) methane-1,2-benzoquinonediazide-4- Sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-benzoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-benzoquinonediazide-4-sulfonic acid ester, tri ( p-hydroxyphenyl) methane-1,2-benzoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-benzoquinonediazide-4-sulfonic acid ester, 1, 1,1-tri (p-hydroxyphenyl) ethane-1,2-benzoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-benzoquinonediazide-4-sulfone Acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2- Nzoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3 , 4-Trihydroxyphenyl) propane-1,2-benzoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2 -Benzoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-benzoquinonediazide-5-sulfonic acid ester, 4, 4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 2-benzoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-benzoquinonediazide— 5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-benzoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxy) Phenyl) -2-hydroxyphenylmethane-1,2-benzoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7, 5 ′, 6 ′, 7′-hexanol-1,2-benzoquinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl 1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-benzoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-Trihydroxyflavan-1,2-benzoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-benzoquinonediazide-5 -A sulfonic acid ester etc. are mentioned.
These may be used alone or in combination of two or more.

Specific examples of 1,2-naphthoquinonediazide sulfonic acid ester include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1, 2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,3 ′ 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 , 4′-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2 , 4-Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4- Sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri ( p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfone Acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2- Phtoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,3) 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2- Naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1 2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide— 5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxy) Phenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7, 5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl 1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-Trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5 -A sulfonic acid ester etc. are mentioned.
These may be used alone or in combination of two or more.

Specific examples of 1,2-benzoquinonediazidesulfonamide include 2,3,4-trihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonamide, 2,3,4-trihydroxybenzophenone-1,2- Benzoquinonediazide-5-sulfonamide, 2,4,6-trihydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonamide, 2,4,6-trihydroxybenzophenone-1,2-benzoquinonediazide-5-sulfone Amides, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-benzoquinonediazide-4-sulfonamide, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-benzoquinonediazide-5 -Sulfonamide, 2,3,3 ', 4-tetrahydroxybenzo Enone-1,2-benzoquinonediazide-4-sulfonamide, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-benzoquinonediazide-5-sulfonamide, 2,3,4,4′-tetrahydroxy Benzophenone-1,2-benzoquinonediazide-4-sulfonamide, 2,3,4,4′-tetrahydroxybenzophenone-1,2-benzoquinonediazide-5-sulfonamide, bis (2,4-dihydroxyphenyl) methane 1,2-benzoquinonediazide-4-sulfonamide, bis (2,4-dihydroxyphenyl) methane-1,2-benzoquinonediazide-5-sulfonamide, bis (p-hydroxyphenyl) methane-1,2-benzoquinonediazide -4-sulfonamide, bis (p-hydroxyphenyl) methane -1,2-benzoquinonediazide-5-sulfonamide, tri (p-hydroxyphenyl) methane-1,2-benzoquinonediazide-4-sulfonamide, tri (p-hydroxyphenyl) methane-1,2-benzoquinonediazide- 5-sulfonamide, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-benzoquinonediazide-4-sulfonamide, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2 -Benzoquinonediazide-5-sulfonamide, bis (2,3,4-trihydroxyphenyl) methane-1,2-benzoquinonediazide-4-sulfonamide, bis (2,3,4-trihydroxyphenyl) methane-1 , 2-Benzoquinonediazide-5-sulfonamide, 2,2-bis (2,3,4-trihydroxy) Phenyl) propane-1,2-benzoquinonediazide-4-sulfonamide, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-benzoquinonediazide-5-sulfonamide, 1,1, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-benzoquinonediazide-4-sulfonamide, 1,1,3-tris (2,5-dimethyl-4-hydroxy Phenyl) -3-phenylpropane-1,2-benzoquinonediazide-5-sulfonamide, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol-1,2-benzoquinonediazide-4-sulfonamide, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-benzoquinonediazide-5-sulfonamide, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-benzoquinonediazide -4-sulfonamide, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-benzoquinonediazide-5-sulfonamide, 3,3,3 ', 3'-tetramethyl -1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-benzoquinonediazide-4-sulfonamide, 3,3,3 ', 3'-tetra Methyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-benzoquinonediazide-5-sulfonamide, 2 2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-benzoquinonediazide-4-sulfonamide, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan- 1,2-benzoquinonediazide-5-sulfonamide and the like.
These may be used alone or in combination of two or more.

Specific examples of 1,2-naphthoquinonediazidesulfonamide include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonamide, 2,3,4-trihydroxybenzophenone-1,2- Naphthoquinonediazide-5-sulfonamide, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonamide, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone Amides, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonamide, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 -Sulfonamide, 2,3,3 ', 4-tetrahydroxybenzo Enone-1,2-naphthoquinonediazide-4-sulfonamide, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonamide, 2,3,4,4′-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-4-sulfonamide, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonamide, bis (2,4-dihydroxyphenyl) methane 1,2-naphthoquinonediazide-4-sulfonamide, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonamide, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide -4-sulfonamide, bis (p-hydroxyphenyl) methane -1,2-naphthoquinonediazide-5-sulfonamide, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonamide, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- 5-sulfonamide, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonamide, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2 -Naphthoquinonediazide-5-sulfonamide, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonamide, bis (2,3,4-trihydroxyphenyl) methane-1 , 2-Naphthoquinonediazide-5-sulfonamide, 2,2-bis (2,3,4-trihydroxy) Phenyl) propane-1,2-naphthoquinonediazide-4-sulfonamide, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonamide, 1,1, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonamide, 1,1,3-tris (2,5-dimethyl-4-hydroxy Phenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonamide, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol-1,2-naphthoquinonediazide-4-sulfonamide, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonamide, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide -4-sulfonamide, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonamide, 3,3,3 ', 3'-tetramethyl -1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonamide, 3,3,3 ', 3'-tetra Methyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5-sulfonamide, 2 2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonamide, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan- 1,2-naphthoquinonediazide-5-sulfonamide and the like.
These may be used alone or in combination of two or more.

  As the 1,2-quinonediazide compound contained in the positive photosensitive composition of the present invention, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-triacid Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1, 2-naphthoquinonediazide-4-sulfonic acid ester and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide— When at least one selected from the group consisting of 5-sulfonic acid esters is used, the transparency of the positive photosensitive composition is improved. Preferred for Kunar.

  The concentration of the 1,2-quinonediazide compound in the positive photosensitive composition of the present invention is not particularly limited, but is preferably 0.5 to 20% by weight from the viewpoint of balance between sensitivity and transparency.

1.4 Epoxy resin (C)
The positive photosensitive composition of the present invention may further contain an epoxy resin (C). The epoxy resin (C) contained in the positive photosensitive composition of the present invention is not particularly limited as long as it has oxirane, but a compound having two or more oxiranes is preferable.
Specific examples of the epoxy resin (C) contained in the positive photosensitive composition of the present invention include a polymer of a monomer having an oxirane, and a copolymer of a monomer having an oxirane and another monomer.

  Specific examples of the monomer having oxirane include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate.

  Specific examples of other monomers copolymerized with the oxirane-containing monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth). Acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, Mention may be made of methylstyrene, chloromethylstyrene, N-cyclohexylmaleimide and N-phenylmaleimide.

  Among these, a polymer of a monomer having oxirane, a copolymer of a monomer having oxirane and another monomer, polyglycidyl methacrylate, methyl methacrylate-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, n It is preferable to use a -butyl methacrylate-glycidyl methacrylate copolymer, a 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer because the resulting positive photosensitive composition has high heat resistance.

  In addition to the above specific examples, the epoxy resin (C) includes, for example, trade names “Epicoat 807”, “Epicoat 815”, “Epicoat 825”, “Epicoat 827”, “Epicoat 828”, “Epicoat 190P”, “Epicoat 191P” (above, manufactured by Yuka Shell Epoxy Co., Ltd.), trade names “Epicoat 1004”, “Epicoat 1256” (above, manufactured by Japan Epoxy Resin Co., Ltd.), products The name “Araldite CY177”, the trade name “Araldite CY184” (manufactured by Ciba Geigy Japan), which is a compound of the above formula (C1), and the trade names “Celoxide 2021P” and “Celoxide 3000” which are compounds of the above formula (C2). "EHPE-3150" (manufactured by Daicel Chemical Industries, Ltd.), a compound of the above formula (C3) "Techmore VG3101L" (Mitsui Chemicals), N, N, N ', N',-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) Cyclohexane, N, N, N ′, N ′,-tetraglycidyl-4,4′-diaminodiphenylmethane and the like can be used.

  Among these epoxy resins (C), use of “Epicoat 828”, “Techmore VG3101”, “Celoxide 2021P”, and “Araldite CY184” is preferable because the resulting positive photosensitive composition has high heat resistance.

  In the present invention, the concentration of the epoxy resin in the positive photosensitive composition is not particularly limited, but is preferably 0.5 to 20% by weight. Within this concentration range, the heat resistance and chemical resistance of the coating film formed from the protective film composition are good.

1.5 Solvent The solvent that can be included in the positive photosensitive composition of the present invention is at least one compound having a boiling point of 100 ° C. to 250 ° C., or a mixed solvent containing 20% by weight or more of this compound. Is preferred. Specific examples of the solvent having a boiling point of 100 ° C. to 250 ° C. are water, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , 2- Ethyl toxipropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, pyrubin Methyl acetate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, 1,4-butanediol, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monome Ether ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, toluene, xylene, γ-butyrolactone, N, N-dimethylacetamide, - methyl-2-pyrrolidone, dimethyl imidazolidinone, and the like.

  Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol Use of at least one selected from dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate, and butyl acetate is more preferable because the coating uniformity becomes high. Further, when at least one selected from propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate and butyl acetate is used, the resulting positive photosensitive composition is This is preferable because the coating uniformity is high and the safety to the human body is increased.

1.6 Additives added to the positive photosensitive composition of the present invention The positive photosensitive composition of the present invention contains various additives to improve resolution, coating uniformity, developability, adhesiveness, and the like. Additives can be added. Additives include acrylic, styrene, polyethyleneimine or urethane polymer dispersants, anionic, cationic, nonionic or fluorine surfactants, silicone resin coating improvers, silane couplings Adhesion improvers such as adhesives, ultraviolet absorbers such as alkoxybenzophenones, anti-aggregation agents such as sodium polyacrylate, thermal cross-linking agents such as epoxy compounds, melamine compounds or bisazide compounds, and alkali solubility promotion such as organic carboxylic acids Agents and the like.

  Specific examples of the additive include trade names “EFKA-745”, “EFKA-46”, “EFKA-47”, “EFKA-47EA”, “EFKA Polymer 100”, “EFKA Polymer 400”, “EFKA Polymer 401”. ”,“ EFKA Polymer 450 ”(Morishita Sangyo Co., Ltd.),“ Solspurs 3000 ”,“ Solspurs 5000 ”,“ Solspurs 9000 ”,“ Solspurs 12000 ”,“ Solspurs 13240 ”,“ Solspurs 13940 ”,“ Solspurs 17000 ”, "Solspurs 20000", "Solspurs 24000", "Solspurs 24000GR", "Solspurs 26000", "Solspurs 28000", "Solspurs 32000" (manufactured by Lubrizol corporation), "Disperse Aid 6", "D "Perth Aid 8", "Disperse Aid 15", "Disperse Aid 9100" (manufactured by San Nopco), "Polyflow No. 45", "Polyflow KL-245", "Polyflow No. 75", "Polyflow No. 75" 90 "," Polyflow No. 95 "(manufactured by Kyoeisha Chemical Industry Co., Ltd.)," Disperbyk 161 "," Disperbyk 162 "," Disperbyk 163 "," Disperbyk " ) 164 ”,“ Disperbyk 166 ”,“ Disperbyk 170 ”,“ Disperbyk 180 ”,“ Disperbyk 181 ”,“ Desperbyk 181 ” Disperbyk 182 ”,“ BYK300 ”,“ BYK306 ”,“ BYK310 ”,“ BYK320 ”,“ BYK330 ”,“ BYK344 ”,“ BYK346 ”(manufactured by BYK Chemie Japan KK),“ Surflon SC-101 ”, “Surflon KH-40” (manufactured by Seimi Chemical Co., Ltd.), “Futgent 222F”, “Futgent 251”, “FTX-218” (manufactured by Neos Co., Ltd.), “EFTOP”, “EF-351”, “EF” -352 "," EF-601 "," EF-801 "," EF-802 "(manufactured by Mitsubishi Materials Corporation)," Megafuck F-171 "," Megafuck F-177 "," Megafuck F- " 475 ”,“ Megafuck R-08 ”,“ Megafuck R-30 ”(Dainippon Ink, Inc.) Manufactured by Gaku Kogyo Co., Ltd.), fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl poly) Oxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene steer Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan Laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, etc., and at least selected from these It is preferable to use one.

  Among these additives, fluoroalkyl benzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene) Oxyethylene ether), fluorosurfactants such as fluoroalkyltrimethylammonium salts, fluoroalkylaminosulfonates, and at least one selected from the group consisting of silicon resin coating improvers such as BYK306, BYK344, BYK346 Addition of seeds is preferable because the coating uniformity of the positive photosensitive composition is increased.

  In the present invention, the concentration of the additive in the positive photosensitive composition is not particularly limited, but is preferably 0.01 to 1% by weight. When the concentration is within this range, the coating uniformity of the formed coating film is good.

1.7 Polyvalent carboxylic acid added to the positive photosensitive composition of the present invention The positive photosensitive composition of the present invention includes trimellitic anhydride, phthalic anhydride, 4-methylcyclohexane-1,2- You may add polyvalent carboxylic acid, such as dicarboxylic acid anhydride. Of these polyvalent carboxylic acids, trimellitic anhydride is preferable.
When the polyvalent carboxylic acid is added to the positive photosensitive composition of the present invention and heated, the carboxyl of the polyvalent carboxylic acid reacts with the epoxy of the positive photosensitive composition, resulting in heat resistance and chemical resistance. Can be improved. Moreover, when the polyvalent carboxylic acid is added to the positive photosensitive composition of the present invention, the decomposition of the 1,2-quinonediazide compound is suppressed during storage, and coloring of the positive photosensitive composition is prevented. it can.
In the present invention, the concentration of the polyvalent carboxylic acid in the positive photosensitive composition is not particularly limited, but the heat resistance and chemical resistance of the coating film of the positive photosensitive composition of the present invention will be 0.2. -10 wt% is preferred.

1-3 Preservation of Positive Type Photosensitive Composition The positive type photosensitive composition of the present invention is preferably stored under light shielding in the temperature range of −30 ° C. to 25 ° C., since the stability with time of the composition is good. More preferably, the storage temperature is −30 ° C. to 10 ° C.

2 Transparent Film Using the Positive Photosensitive Composition of the Present Invention The second aspect of the present invention relates to a transparent film and a patterned transparent film formed from the positive photosensitive composition of the present invention.

The transparent film of the present invention is formed as follows.
First, the positive photosensitive composition of the present invention is applied onto a substrate such as glass by a known method such as spin coating, roll coating, slit coating or the like. Examples of substrates include transparent glass substrates such as white plate glass, blue plate glass, and silica coated blue plate glass, synthetic resins such as polycarbonate, polyethersulfone, polyester, acrylic resin, vinyl chloride resin, aromatic polyamide resin, polyamideimide, and polyimide. Examples thereof include a sheet made of synthetic resin, a film made of synthetic resin or a substrate made of synthetic resin, a metal substrate such as an aluminum plate, a copper plate, a nickel plate and a stainless plate, a ceramic plate, and a semiconductor substrate having a photoelectric conversion element. If necessary, these substrates can be subjected to pretreatment such as chemical treatment such as a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum deposition.

Next, this board | substrate is normally dried at 60-120 degreeC for 1 to 5 minutes with a hotplate or oven. The dried substrate is irradiated with ultraviolet rays through a mask having a desired pattern shape. Irradiation conditions are preferably 5 to 1000 mJ / cm ^{2 for} i-line.
The 1,2-quinonediazide compound in the portion irradiated with ultraviolet rays becomes indenecarboxylic acid and dissolves rapidly in the developer. The developer used at this time is preferably an alkaline solution. Specific examples of the alkali contained in the alkaline solution include tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide, water Potassium oxide and the like. As the developer, an aqueous solution of these alkalis is preferably used. Among these, as developers, aqueous solutions of organic alkalis such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, and sodium carbonate, sodium hydroxide, potassium hydroxide, etc. An aqueous solution of an inorganic alkali is preferable.

  For the purpose of reducing the development residue and optimizing the pattern shape, methanol, ethanol or a surfactant may be added to the developer. The surfactant to be added can be selected from, for example, anionic, cationic and nonionic. Among these, the addition of nonionic polyoxyethylene alkyl ether is particularly preferable because the resolution is increased.

After developing using a general development method (shower development, spray development, paddle development, dip development, etc.), rinse thoroughly with pure water, and then again irradiate the entire surface of the substrate with an intensity of 100 to 1000 mJ / cm ² . When irradiated and finally baked at 180 to 250 ° C. for 10 to 120 minutes, a desired patterned transparent film (patterned transparent film) of the present invention can be obtained.

  The transparent film and patterned transparent film of the present invention thus obtained can be used as a photosensitive protective film because of high transparency and heat resistance and excellent foreign matter characteristics.

  The transparent film of the present invention can also be used as an insulating film. Here, the insulating film refers to, for example, a film (interlayer insulating film) provided to insulate the wirings arranged in layers. The transparent film of a preferred embodiment of the present invention has high resolution during patterning, and can form an insulating film having a small hole of 10 μm or less. The shape of the hole formed in the patterned transparent film (patterned insulating film) of the present invention is preferably, for example, a square, a rectangle, a circle or an ellipse when viewed from directly above. Furthermore, a transparent electrode may be formed over the insulating film, and after patterning by etching, a film for performing an alignment process may be formed. Since the insulating film according to a preferred embodiment of the present invention has high sputter resistance, wrinkles are hardly generated in the insulating film even when a transparent electrode is formed, and high transparency can be maintained.

3. Display Element Comprising Transparent Film or Insulating Film of the Present Invention A third aspect of the present invention relates to a display element including the patterned patterned transparent film or insulating film of the present invention.

A liquid crystal display element which is an embodiment of the display element of the present invention includes an element substrate provided with a transparent film or an insulating film patterned on a substrate as described above, and a color filter substrate which is a counter substrate. Are combined by heat treatment, injecting liquid crystal, and sealing the injection port.
Further, after the liquid crystal is spread on the element substrate, the liquid crystal display element may be manufactured by superimposing the substrates and sealing the liquid crystal so as not to leak.
In this way, a protective film or insulating film having excellent transparency and formed of the positive photosensitive composition of the present invention can be used for a liquid crystal display element.

  The liquid crystal composition used in the liquid crystal display element of the present invention is not particularly limited, and various liquid crystal compositions having positive dielectric anisotropy can be used. Examples of preferred liquid crystal compositions include Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8-231960, and Japanese Patent Laid-Open No. 9-241644. (EP885272A1 specification), JP-A-9-302346 (EP806466A1 specification), JP-A-8-199168 (EP722998A1 specification), JP-A-9-235552, JP-A-9-255958, JP-A-9-241463 (EP885271A1), JP-A-10-204016 (EP844229A1), JP-A-10-204436, JP-A-10-231482, JP-A-2000-087040, JP Opened in Gazette 2001-48822 It is.

  Various liquid crystal compositions having negative dielectric anisotropy can also be used. Examples of preferred liquid crystal compositions include JP-A-57-141432, JP-A-2-4725, JP-A-4-224858, JP-A-8-40953, JP-A-8-104869, Japanese Laid-Open Patent Publication No. 10-168076, Japanese Laid-Open Patent Publication No. 10-168453, Japanese Laid-Open Patent Publication No. 10-236989, Japanese Laid-Open Patent Publication No. 10-236990, Japanese Laid-Open Patent Publication No. 10-236992, Japanese Laid-Open Patent Publication No. 10-236993, Japanese Laid-open Patent Publication No. -236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, JP-A-10-237035, JP-A-10-237075, JP-A-10-237076 JP, 10-237448, (EP967261A1), JP 10-28. 874, JP-A-10-287875, JP-A-10-291945, JP-A-11-029581, JP-A-11-080049, JP-A-2000-256307, JP-A-2001-019965, JP-A-2001-072626, JP-A-2001-192657, and the like.

  One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example and a comparative example, this invention is not limited to these Examples.

  The names of anhydrides, diamines, and solvents used in Examples and Comparative Examples are abbreviated. This abbreviation is used in the following description.

Compound (a1) having two or more acid anhydride groups
Styrene-maleic anhydride copolymer (copolymerization molar ratio 1: 1, weight average molecular weight 1,100): SMA
3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride: ODPA
Diamine (a2)
3,3′-Diaminodiphenylsulfone: DDS
Solvent Methyl 3-methoxypropionate: MMP
Diethylene glycol methyl ethyl ether: EDM

[Synthesis Example 1] Synthesis of Compound (A1-1) A 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet was charged with raw materials as shown below, and a dry nitrogen stream The mixture was stirred at 130 ° C. for 5 hours to obtain a 30% by weight solution of compound (A1-1), which is a pale yellow transparent polyester.
MMP 286.5g
SMA 70.7g
ODPA 23.3g
1,4-butanediol 18.0g
Benzyl alcohol 10.8g

  The viscosity of this solution was 88 mPa · s. The weight average molecular weight measured by GPC was 15,000.

[Synthesis Example 2] Synthesis of Compound (A2-1) Into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, the raw materials were charged as shown below, under a dry nitrogen stream The mixture was stirred at 130 ° C. for 2 hours.
MMP 276.0g
SMA 70.7g
ODPA 23.3g
1,4-butanediol 13.5g
Benzyl alcohol 10.8g

The solution after the above reaction was cooled to 40 ° C., and the following compounds were additionally added, stirred at 40 ° C. for 2 hours, further heated to 120 ° C. and stirred for 1 hour, and a pale yellow transparent polyester-polyamic acid As a result, a 30 wt% solution of the compound (A2-1) was obtained.
MMP 29.0g
DDS 12.4g

  The viscosity of this solution was 117 mPa · s. The weight average molecular weight measured by GPC was 19,000.

[Synthesis Example 3] Synthesis of Compound (A2-2) Raw materials were charged as shown below into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet, and a nitrogen gas inlet, and a dry nitrogen stream was used. The mixture was stirred at 130 ° C. for 2 hours.
MMP 181.8g
ODPA 62.0g
1,4-butanediol 7.2 g
8.7 g of benzyl alcohol

The solution after the above reaction was cooled to 40 ° C., and the following compounds were additionally added, stirred at 40 ° C. for 2 hours, further heated to 120 ° C. and stirred for 1 hour, and a pale yellow transparent polyester-polyamic acid As a result, a 30 wt% solution of the compound (A2-2) was obtained.
MMP 46.4g
DDS 19.9g

  The viscosity of this solution was 43 mPa · s. The weight average molecular weight measured by GPC was 9,000.

[Comparative Synthesis Example 1] (Synthesis Example 1 of JP-A-2002-287351)
A raw material was charged as shown below into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging inlet and a nitrogen gas inlet, and stirred at 70 ° C. for 5 hours while bubbling dry nitrogen.
EDM 220.0g
Styrene 20.0g
Methacrylic acid 20.0g
Glycidyl methacrylate 40.0g
2-Hydroxyethyl methacrylate 20.0g
2,2′-azobis (2,4-dimethylvaleronitrile) 8.0 g

  The viscosity of this solution was 33 mPa · s. The weight average molecular weight measured by GPC was 11,000. The polymer concentration determined from loss on drying at 170 ° C. was 30.1% by weight.

[Example 1] Preparation of positive photosensitive composition 4,4 '-[1- [4- [1- [4] as the compound (A1-1) obtained in Synthesis Example 1 and 1,2-quinonediazide compound 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 4,4 ′-[1- [4- [1- [4] -Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate 58%, hereinafter abbreviated as "PAD"), fluorine-based interface as additive “Surflon SC-101” (manufactured by Seimi Chemical Co., Ltd., hereinafter abbreviated as “SC-101”) as an activator and MMP as a solvent are mixed in the following weights. Construed, to obtain a positive photosensitive composition.
MMP 1.40g
10.00 g of 30% by weight solution of compound (A1-1)
PAD 0.60g
SC-101 0.006g

  The positive photosensitive composition thus obtained was evaluated for heat resistance, flatness and foreign matter characteristics.

(1) Heat resistance The positive photosensitive composition prepared in Example 1 on a glass substrate was spin-coated at 800 rpm for 10 seconds and dried on a hot plate at 100 ° C. for 2 minutes. This substrate is passed through a mask for hole pattern formation in the air using a Topcon Co., Ltd. proximity exposure machine “TME-150PRC”, and the light of 350 nm or less is cut through a wavelength cut filter to make g, h, i The line was taken out and exposed with an exposure gap of 100 μm. The exposure amount was 100 mJ / cm ² measured with an integrated light meter “UIT-102” and a photoreceiver “UVD-365PD” manufactured by USHIO INC. The exposed glass substrate was dip-developed with a 0.3 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds to remove the exposed portion. The substrate after development was washed with pure water for 60 seconds and then dried on a hot plate at 100 ° C. for 2 minutes. The entire surface of the substrate was exposed at an exposure amount of 300 mJ / cm ² without using a mask with the exposure machine, and then post-baked in an oven at 230 ° C. for 30 minutes to form a patterned transparent film having a thickness of 3 μm. For the film thickness, a stylus type film thickness meter “α step 200” manufactured by KLA-Tencor Japan Co., Ltd. was used, and the average value of the measurements at three locations was taken as the film thickness. This substrate was further heated in an oven at 240 ° C. for 1 hour, and then the film thickness was measured again, and the rate of change in film thickness before and after the additional heating was calculated from the following equation.
[(Film thickness after additional heating−film thickness before additional heating) / film thickness before additional heating] × 100 (%)
The results are shown in Table 1. It shows that heat resistance is so good that this value is small.

(2) Flatness The positive photosensitive composition prepared in Example 1 was spin-coated at 800 rpm for 10 seconds on a color filter substrate with a black matrix and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was dipped in a 0.3 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, further washed with pure water for 60 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. The entire surface of the substrate was exposed at an exposure amount of 300 mJ / cm ² without using a mask with the exposure machine, and then post-baked in an oven at 230 ° C. for 30 minutes to obtain a color filter substrate with a protective film. The maximum level difference was measured on the substrate using the film thickness meter. Here, the “maximum step” refers to the difference between the highest point and the lowest point when the measurement length is set to 400 μm and the unevenness of the substrate surface is continuously measured. The average value of the three maximum steps measured on the substrate was taken as the maximum step after forming the protective film. The same measurement was performed on a black matrix without a protective film. This value was defined as the maximum level difference before forming the protective film. The flattening rate after forming the protective film was calculated from the following equation.
((Maximum step before protective film formation-maximum step after protective film formation) / maximum step before protective film formation) x 100 (%)
The results are shown in Table 1. The larger this value, the better the flatness.
(3) Foreign material characteristics On a glass substrate with a chromium film, bead spacers having a diameter of 20 μm were spread using a bead spacer spreader so as to be 3 to 5 pieces / cm ² . On this substrate, the positive photosensitive composition prepared in Example 1 was spin-coated at 800 rpm for 10 seconds and dried on a hot plate at 100 ° C. for 2 minutes. This substrate was dipped in a 0.3 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, further washed with pure water for 60 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. The entire surface of the substrate was exposed at an exposure amount of 300 mJ / cm ² without using a mask by the exposure machine, and then post-baked in an oven at 230 ° C. for 30 minutes to obtain a substrate for foreign material property evaluation. This substrate was observed with an optical microscope, and the diameter of interference fringes generated around the beads was measured.
The results are shown in Table 1. The smaller the interference fringe diameter, the better the foreign matter characteristics.

[Example 2]
A positive photosensitive composition was prepared in the same manner as in Example 1 except that the compound (A2-1) obtained in Synthesis Example 2 was used instead of the compound (A1-1), and the composition was evaluated. .
The results are shown in Table 1.

[Example 3]
A positive photosensitive composition was prepared and evaluated in the same manner as in Example 1 except that the compound (A2-2) obtained in Synthesis Example 3 was used instead of the compound (A1-1).
The results are shown in Table 1.

[Comparative Example 1]
A positive photosensitive composition was prepared and evaluated in the same manner as in Example 1 except that the polymer obtained in Comparative Synthesis Example 1 was used instead of the compound (A1-1). The results are shown in Table 1.

  The positive photosensitive composition of the present invention can be used as a color filter protective film for a liquid crystal display element or an insulating film for a TFT substrate.

Claims (22)

Following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A positive photosensitive composition containing a compound (A1) having a structural unit represented by formula (1) and a 1,2-quinonediazide compound.   The positive photosensitive composition according to claim 1, wherein the compound (A1) is synthesized using at least the compound (a1) having two or more acid anhydride groups and the polyvalent hydroxy compound (a3). The compound (a1) having two or more acid anhydride groups is selected from the group consisting of tetracarboxylic dianhydrides and copolymers of polymerizable monomers having acid anhydride groups and other polymerizable monomers. 1 or more,
The positive photosensitive composition according to claim 2, wherein the polyvalent hydroxy compound (a3) is a diol. Compound (A1) is
Reaction product of diol, tetracarboxylic dianhydride and styrene-maleic anhydride copolymer,
Reaction product of diol and tetracarboxylic dianhydride, or
The positive photosensitive composition according to claim 1, which is a reaction product of a diol and a styrene-maleic anhydride copolymer. Compound (A1) is
Reaction product of diol, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monohydric alcohol,
Reaction product of diol, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monoamine,
Reaction product of diol, tetracarboxylic dianhydride and monohydric alcohol,
Reaction products of diols, tetracarboxylic dianhydrides and monoamines,
Reaction product of diol, styrene-maleic anhydride copolymer and monohydric alcohol, or
The positive photosensitive composition according to claim 1, which is a reaction product of a diol, a styrene-maleic anhydride copolymer and a monoamine. The diol is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Two or more
Tetracarboxylic dianhydride is pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride One or more selected from the group consisting of things,
Monohydric alcohols are benzyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, propylene glycol monoethyl ether, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxy One or more selected from the group consisting of methyl oxetane,
Monoamine is 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxy Silane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxy The positive photosensitive composition according to claim 4 or 5, which is one or more selected from the group consisting of silane, m-aminophenylmethyldiethoxysilane, and aminobenzoic acid. Following formula (1)

(In the formula, R ¹ and R ² are each independently an organic group having 2 to 100 carbon atoms.)
And the following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A positive photosensitive composition containing a compound (A2) having a structural unit represented by formula (1) and a 1,2-quinonediazide compound.   The positive type according to claim 7, wherein the compound (A2) is synthesized using at least the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3). Photosensitive composition. The compound (a1) having two or more acid anhydride groups is selected from the group consisting of tetracarboxylic dianhydrides and copolymers of polymerizable monomers having acid anhydride groups and other polymerizable monomers. 1 or more,
The positive photosensitive composition according to claim 8, wherein the polyvalent hydroxy compound (a3) is a diol. Compound (A2) is
Reaction product of diol, diamine, tetracarboxylic dianhydride and styrene-maleic anhydride copolymer,
Reaction product of diol, diamine and tetracarboxylic dianhydride, or
Reaction product of diol, diamine and styrene-maleic anhydride copolymer,
The positive photosensitive composition according to claim 7, wherein Compound (A2) is
Reaction product of diol, diamine, tetracarboxylic dianhydride, styrene-maleic anhydride copolymer and monohydric alcohol,
Reaction products of diols, diamines, tetracarboxylic dianhydrides, styrene-maleic anhydride copolymers and monoamines,
Reaction product of diol, diamine, tetracarboxylic dianhydride and monohydric alcohol,
Reaction products of diols, diamines, tetracarboxylic dianhydrides and monoamines,
Reaction product of diol, diamine, styrene-maleic anhydride copolymer and monohydric alcohol, or
Diol, diamine, styrene-maleic anhydride copolymer, monoamine reaction product,
The positive photosensitive composition according to claim 7, wherein The diol is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. Two or more
Diamine is 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3 ′. -Dimethyl-4,4'-diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-diaminodiphenylpropane, bis [4- (4-aminobenzyl) Phenyl] methane and the following formula (A)

Wherein R ⁴ and R ⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ^{6 is} independently methylene, phenylene or alkyl-substituted phenylene. X is independently 1 to 1 6 is an integer, and y is an integer of 1 to 10.)
One or more selected from the group consisting of compounds represented by:
Tetracarboxylic dianhydride is pyromellitic dianhydride, cyclobutanetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride One or more selected from the group consisting of things,
The monohydric alcohol is one or more selected from the group consisting of benzyl alcohol, 2-hydroxyethyl methacrylate, propylene glycol monoethyl ether, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane;
The monoamine is one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-aminobenzoic acid The positive photosensitive composition according to claim 10 or 11, which is as described above. The diol is 1,4-butanediol;
Diamine is 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, and the following formula (A)

Wherein R ⁴ and R ⁵ are independently alkyl or phenyl having 1 to 3 carbon atoms, R ^{6 is} independently methylene, phenylene or alkyl-substituted phenylene. X is independently 1 to 1 6 is an integer, and y is an integer of 1 to 10.)
One or more selected from the group consisting of compounds represented by:
Tetracarboxylic dianhydrides are pyromellitic dianhydride, butanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4. One or more selected from the group consisting of '-diphenyl ether tetracarboxylic dianhydride,
The monohydric alcohol is one or more selected from the group consisting of benzyl alcohol, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane;
The monoamine is one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane, and aminobenzoic acid. Positive photosensitive composition. A compound (a1) having two or more acid anhydride groups selected from the group consisting of a reaction product of tetracarboxylic dianhydride and styrene-maleic anhydride copolymer, ethylene glycol, propylene glycol , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol (A3) and the following formula (2) synthesized using

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A compound (A1) having a structural unit represented by:
A positive photosensitive composition containing a 1,2-quinonediazide compound. A compound (a1) having two or more acid anhydride groups which are one or more selected from the group consisting of a reaction product of tetracarboxylic dianhydride and styrene-maleic anhydride copolymer, and 4,4′- Diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′- Selected from the group consisting of diaminodiphenylmethane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-diaminodiphenylpropane and bis [4- (4-aminobenzyl) phenyl] methane One or more diamines (a2), ethylene glycol, propylene glycol, 1,4-butane A polyhydric hydroxy compound (a3) which is at least one selected from the group consisting of diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol; The following formula (1)

(In the formula, R ¹ and R ² are each independently an organic group having 2 to 100 carbon atoms.)
And the following formula (2)

(In the formula, R ¹ and R ³ are each independently an organic group having 2 to 100 carbon atoms.)
A compound (A2) having a structural unit represented by:
A positive photosensitive composition containing a 1,2-quinonediazide compound.   1,2-quinonediazide compound is 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester The positive photosensitive composition according to claim 1, wherein the positive photosensitive composition is one or more.   1,2-quinonediazide compound is 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid esters and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid esters The positive photosensitive composition according to claim 1, which is one or more selected from the group consisting of:   Furthermore, the positive photosensitive composition of Claims 1-17 containing an epoxy resin (C). The positive photosensitive composition according to claim 17, wherein the epoxy resin (C) is one or more selected from compounds represented by the following formulas (C1) to (C4).

(In the formula, n is an integer of 0 to 10.)   The positive type resin according to claim 18, wherein the epoxy resin (C) is at least one selected from the group consisting of a polymer of a monomer having an oxirane and a copolymer of a monomer having an oxirane and another monomer. Photosensitive composition.   The positive photosensitive composition according to claim 18, wherein the monomer having oxirane is one or more selected from glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate. .   The transparent film or pattern-shaped transparent film of the positive photosensitive composition of any one of Claims 1-21.