JP2018035340A - Polyester amide acid and photosensitive composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester amide acid which becomes a component of a photosensitive composition excellent in resolution and a residual film ratio.SOLUTION: A polyester amide acid (A) is a reactive product from a raw material containing a tetracarboxylic acid dianhydride, diamine, a polyvalent hydroxy compound and a cationic polymerizable cyclic ether compound having a polymerizable double bond, where the polyester amide acid (A) contains X mol of the tetracarboxylic acid dianhydride, Y mol of the diamine, Z mol of the polyvalent hydroxy compound, and W mol of the cationic polymerizable cyclic ether compound having the polymerizable double bond with a ratio satisfying a relationship of expression (1): 0.2≤Z/Y≤8.0, expression (2): 0.2≤(Y+Z)/X≤5.0, and expression (3): 0.05≤W/2X≤1.0.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive polymer and a photosensitive composition containing the photosensitive polymer. The present invention relates to a cured film formed from the photosensitive composition, a color filter using the cured film, an insulating film, or a protective film. Furthermore, this invention relates to the manufacturing method of this photosensitive polymer.

Elements such as display elements are subjected to chemical treatment or high-temperature heat treatment on the surface in a normal manufacturing process. In order to prevent deterioration, damage, and alteration due to the treatment, a protective film is provided on the surface of the element. The protective film is required to have good resolution and residual film ratio as well as heat resistance, chemical resistance, adhesion to the substrate, transparency, flatness and the like.

In order to form the protective film, roughly, a thermosetting composition or a photosensitive composition is used. In the case of a thermosetting composition, the volatile matter generated at the time of film formation is reduced, and the heat resistance is excellent. However, when a thermosetting composition is used, it is difficult to form a scribe line, and a cleaning process for debris generated during panel division is required.

On the other hand, when using a photosensitive composition, formation of a scribe line is easy and it is excellent in a moldability. Therefore, needs for forming a protective film are increasing for a photosensitive composition capable of being finely molded (finely patterned).

However, in order to form an excellent fine pattern shape, the photosensitive composition is required to have an appropriate balance between the resolution and the remaining film ratio while maintaining appropriate solubility in a developer. The If the solubility of the unexposed part is increased in order to improve the resolution, the solubility of the exposed part also increases and the remaining film ratio decreases. On the other hand, if the solubility of the exposed portion is lowered in order to increase the remaining film ratio, the solubility of the unexposed portion is also lowered and the resolution is lowered. That is, it is necessary to select an appropriate composition ratio of the photosensitive composition so that the solubility of the exposed part is high and the solubility of the unexposed part is low, but the alkali-soluble resin, the photopolymerization initiator, the solvent It is difficult to balance the resolution and the remaining film ratio only by adjusting the types and composition ratios of members constituting the ordinary photosensitive composition such as additives. Therefore, in recent years, studies have been actively conducted to obtain a balance between the resolution and the remaining film ratio by introducing a photosensitive group into the polymer which is the base of the composition.

For example, as shown in Patent Document 1, Patent Document 2 and Patent Document 3, the development of a photosensitive polymer that introduces a polymerizable double bond into a polyimide precursor and imparts an appropriate balance between resolution and residual film ratio. Has been tried. However, for photosensitive compositions containing these photosensitive polymers, there is no description of resolution sizes that can be implemented in the literature, and the manufacturing process of the photosensitive polymer is a complicated system, and it is used depending on the manufacturing conditions. There is room for improvement, such as limited possible raw materials.

JP 2005-154643 A JP 2006-291221 A JP 2006-193691 A

The subject of this invention is providing the polyester amide acid used as the structural component of the photosensitive composition excellent in resolution and a residual film rate.

As a result of diligent studies to solve the above problems, the present inventors have found that tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, and cationic polymerizable cyclic ether compound having a polymerizable double bond are essential raw material components. It was found that the photosensitive composition containing the polyester amide acid as described above has an excellent balance between resolution and remaining film ratio while maintaining appropriate solubility in a developing solution, and the present invention has been completed. The present invention includes the following configurations.

[1] A reaction product from a raw material containing a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond,
In the raw material, X mole of tetracarboxylic dianhydride, Y mole of diamine, Z mole of polyvalent hydroxy compound and W mole of cationic polymerizable cyclic ether compound having a polymerizable double bond are represented by the following formula (1). ), The polyester amic acid (A), which is contained in such a ratio that the relations of the formulas (2) and (3) are established.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / 2X ≦ 1.0 (3)

[2] A reaction product from the raw material further comprising a compound having three or more acid anhydride groups,
In the raw material, X mol of tetracarboxylic dianhydride, Y mol of diamine, Z mol of polyhydroxy compound, W mol of cationic polymerizable cyclic ether compound having a polymerizable double bond, and V mol of acid anhydride The polyester amide acid (A) according to item [1], which contains a compound having 3 or more groups in a ratio such that the relationship of the following formula (1), formula (2) and formula (3 ′) is satisfied;

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / (2X + rV) ≦ 1.0 (3 ′)

The compound having 3 or more acid anhydride groups contains r acid anhydride groups per molecule, and is 0.1% with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. Use ~ 500 parts by weight.

上記式中、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、Ｒ^５は独立してＨ又は重合性二重結合を有する基であり、そして、
前記ポリエステルアミド酸（Ａ）中のＲ^５がすべてＨであることはない。 [3] Polyesteramic acid (A) according to item [1] or [2], comprising a structural unit represented by the following formula (4) and a structural unit represented by formula (5);

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, R ⁵ is independently H or a group having a polymerizable double bond, and
R ⁵ in the polyester amic acid (A) is not all H.

[4] The polyester amide acid (A) according to item [1] or [2], wherein the raw material further contains a monohydroxy compound.

上記式中、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から−ＯＨを除いた残基であり、Ｒ^５は独立してＨ又は重合性二重結合を有する基であり、そして、
前記ポリエステルアミド酸（Ａ）中のＲ^５がすべてＨであることはない。 [5] The polyesteramic acid according to item [4], comprising a structural unit represented by the following formula (4), a structural unit represented by the formula (5), and a structural unit represented by the formula (6): A);

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing —OH from a monohydroxy compound, and R ⁵ independently represents H or a polymerizable double bond. A group having and
R ⁵ in the polyester amic acid (A) is not all H.

[6] The cationic polymerizable cyclic ether compound having a polymerizable double bond has a (meth) acryloxy group, and
The polyester amide acid (A) according to the item [1], [2] or [4], which has a glycidyl group or an oxetanyl group.

[7] The cationic polymerizable cyclic ether compound having a polymerizable double bond is glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7. -Epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- Acrylic esters such as (2-acryloyloxyethyl) oxetane and 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3 -D It is at least one chosen from the group consisting of Ruokisetan, [1] to claim [2] or [4] polyester amide acid according to item (A).

[8] The tetracarboxylic dianhydride includes 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2 , 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound selected from the group consisting of:
The diamine is at least one of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;
The polyvalent hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, 2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, tris (2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) The polyester amide acid (A) according to item [1], [2] or [4], which is at least one selected from the group consisting of ethanol.

[9] The polyester amide acid (A) according to item [2] or [4], wherein the compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer.

[10] The item according to item [4], wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Polyester amide acid (A).

[11] The polyesteramic acid (A) according to any one of [1] to [10], a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), and an epoxy compound (D) And a photosensitive composition comprising an additive (E).

[12] The photosensitive composition according to item [11], wherein the polyester amic acid (A) has a weight average molecular weight of 1,000 to 200,000.

The polyester amide acid according to the embodiment of the present invention constitutes a photosensitive composition excellent in resolution and residual film ratio as well as heat resistance, transparency and flatness by introducing a polymerizable double bond. be able to. And the cured film formed with this photosensitive composition can be applied to various uses, such as a color filter, a protective film, and an insulating film.

1. Polyester amide acid (A)
The polyester amic acid (A) according to an embodiment of the present invention is a reaction product from a raw material containing a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a cationic polymerizable cyclic ether compound having a polymerizable double bond. It is a thing. The raw materials include X-mol tetracarboxylic dianhydride, Y-mol diamine, Z-mol polyvalent hydroxy compound, and a cationic polymerizable cyclic ether compound having W mol-polymerizable double bond, It is included at such a ratio that the relationships of Formula (1), Formula (2), and Formula (3) are established.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / 2X ≦ 1.0 (3)

In the present specification, for the purpose of clarifying the structural characteristics of the polyester amide acid (A) in comparison with other materials used in combination, “polyester amide acid having a polymerizable double bond” is used. (A) ".

The polyester amic acid (A) may be a reaction product from the raw material further containing a compound having 3 or more acid anhydride groups. In that case, in the raw material, X mol of tetracarboxylic dianhydride, Y mol of diamine, Z mol of polyvalent hydroxy compound, W mol of cationic polymerizable cyclic ether compound having a polymerizable double bond, and V mol The compound having 3 or more acid anhydride groups is contained in such a ratio that the relationship of the following formula (1), formula (2) and formula (3 ′) is established.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / (2X + rV) ≦ 1.0 (3 ′)

The compound having 3 or more acid anhydride groups contains r acid anhydride groups per molecule, and is 0.1% with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. Use ~ 300 parts by weight.

上記式中、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、Ｒ^５は独立してＨ又は重合性二重結合を有する基である。そして、前記ポリエステルアミド酸（Ａ）中のＲ^５がすべてＨであることはない。 The polyester amic acid (A) has a structural unit represented by the following formula (4) and a structural unit represented by the formula (5).

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, and R ⁵ is independently H or a group having a polymerizable double bond. And not all R ⁵ in the said polyester amide acid (A) is H.

上記式中、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、Ｒ^４はモノヒドロキシ化合物から−ＯＨを除いた残基であり、Ｒ^５は独立してＨ又は重合性二重結合を有する基である。そして、前記ポリエステルアミド酸（Ａ）中のＲ^５がすべてＨであることはない。 The polyester amide acid (A) according to another embodiment of the present invention is a reaction product from the raw material further containing a monohydroxy compound. In this case, the raw material may or may not contain a compound having three or more acid anhydride groups. The polyester amide acid (A) in this case has a structural unit represented by the following formula (4), a structural unit represented by the formula (5), and a structural unit represented by the formula (6).

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing —OH from a monohydroxy compound, and R ⁵ independently represents H or a polymerizable double bond. It is group which has. And not all R ⁵ in the said polyester amide acid (A) is H.

At least a solvent is required for the synthesis of the polyester amide acid (A) according to the embodiment of the present invention. The solvent may be left as it is, and it may be a liquid or gel photosensitive composition in consideration of handling properties, or may be a solid photosensitive composition in consideration of transportability by removing this solvent.

Moreover, the synthesis | combination of the said polyester amide acid (A) may contain other compounds other than the above in the range which does not impair the objective of this invention.

1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining the polyester amide acid (A). Specific examples of the tetracarboxylic dianhydride are preferably 4,4′-diphenyl ether tetracarboxylic dianhydride (hereinafter sometimes abbreviated as ODPA), 1, 2, 3, used in the examples. 4-butanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as BT-100).

Examples of the tetracarboxylic dianhydride that can be used in the present invention include 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ in addition to the above-described compounds. -Benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 2,2 ' , 3,3′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylethertetracarboxylic dianhydride 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3 -Dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydro trimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic And acid dianhydrides, cyclopentanetetracarboxylic dianhydrides, cyclohexanetetracarboxylic dianhydrides, ethanetetracarboxylic dianhydrides, and butanetetracarboxylic dianhydrides. At least one of the anhydrides can be used.

Among these, tetracarboxylic dianhydrides that give good transparency to the cured film are 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG -100, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 1,2,3,4- Butanetetracarboxylic dianhydride is preferred.

1-2. Diamine In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). Specific examples of diamines preferably include 3,3′-diaminodiphenyl sulfone (hereinafter sometimes abbreviated as DDS) used in the examples.

Specific examples of the diamine that can be used in the present invention include 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl, in addition to the above-described compounds. ] 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, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. And at least one of the diamines can be used.

Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable from the viewpoint of giving good transparency to the cured film, and 3,3′-diaminodiphenylsulfone. Is more preferable.

1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining the polyester amide acid (A). Specific examples of the polyvalent hydroxy compound are preferably 1,4-butanediol used in the examples.

As polyvalent hydroxy compounds that can be used in the present invention, in addition to the above-mentioned compounds, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene Glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-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-heptanedi 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, , 2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecane Diol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol F (bi (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) Examples include ethanol, diethanolamine, and triethanolamine, and at least one of the polyvalent hydroxy compounds described above can be used.

Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, isocyanuric acid tris ( 2-hydroxyethyl), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, This is preferable because of good solubility in the reaction solvent.

1-4. Cationic polymerizable cyclic ether compound having a polymerizable double bond In the present invention, a cationic polymerizable cyclic ether compound having a polymerizable double bond is used as a material for obtaining the polyester amic acid (A). The cationically polymerizable cyclic ether compound having a polymerizable double bond is a compound having a (meth) acryloxy group and having a glycidyl group or an oxetanyl group. Specific examples of the cationic polymerizable cyclic ether compound having a polymerizable double bond are preferably glycidyl methacrylate (hereinafter sometimes abbreviated as GMA) used in the examples, 4-hydroxybutyl acrylate glycidyl ether (hereinafter referred to as GMA). 4HBAGE may be abbreviated as 4).

Specific examples of the cationically polymerizable cyclic ether compound having a polymerizable double bond that can be used in the present invention include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl, in addition to the above-described compounds. Acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, 4-epoxycyclohexylmethyl methacrylate;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- Acrylic esters such as (2-acryloyloxyethyl) oxetane and 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3 -D Ruokisetan can be cited, it is possible to use at least one kind of these.

1-5. Compound having 3 or more acid anhydride groups In the present invention, a compound having 3 or more acid anhydride groups may be used as a material for obtaining the polyester amic acid (A). This is preferable because the transparency of the cured film is improved. The compound having 3 or more acid anhydride groups contains r acid anhydride groups per molecule, and r is 3 to 50, preferably 3 to 25, and more preferably 5 to 10.

As an example of a compound having three or more acid anhydride groups, a styrene-maleic anhydride copolymer can be raised. The ratio (molar ratio) of each component constituting the styrene-maleic anhydride copolymer is styrene / maleic anhydride = 0.5-4, preferably 1-3. Furthermore, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names: Kawa Crude Chemical Co., Ltd.). Among these, SMA1000P, in which the cured film has good heat resistance and alkali resistance, is particularly preferable.

The styrene-maleic anhydride copolymer is preferably contained in an amount of 0.1 to 500 parts by weight per 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. More preferably, it is 10 to 300 parts by weight.

1-6. Monohydroxy Compound In the present invention, a monohydroxy compound may be used as a material for obtaining the polyester amide acid (A). When a monohydroxy compound is used, the storage stability of the photosensitive composition is improved.

Preferable examples of the monohydroxy compound include benzyl alcohol used in the examples.

As monohydroxy compounds that can be used in the present invention, in addition to the above-mentioned compounds, isopropyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol mono Mention may be made of ethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethylbenzyl carbinol.

Among these, benzyl alcohol is particularly preferably used for the monohydroxy compound in consideration of applicability to a color filter when a photosensitive composition is used.

The monohydroxy compound is preferably reacted in an amount of 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

1-7. Monoamine having alkoxysilyl In the synthesis of the polyester amide acid (A) of the present invention, as a raw material, other raw materials other than those described above may be included as necessary, as long as the object of the present invention is not impaired. Examples of the raw material include monoamines having alkoxysilyl.

Specific examples of monoamines having alkoxysilyl used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane. 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, Mention may be made of p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of these can be used.

Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which have good acid resistance of the cured film, are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoints of acid resistance and compatibility. preferable.

The monoamine having alkoxysilyl is preferably contained in an amount of 0 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. Part.

In order to introduce a silyl group at the terminal by reacting with an acid anhydride group at the molecular terminal under the condition where X is excessively used with respect to Y + Z within the range of the above formula (2), the monoamine having alkoxysilyl is introduced. Can be added. When the photosensitive composition containing the polyester amide acid (A) obtained by adding the monoamine which has alkoxy silyl is used, the acid resistance of a cured film will improve.

1-8. In the synthesis of the basic catalyst polyester amic acid (A), as a raw material, other raw materials other than the above may be included as necessary, as long as the purpose of the present invention is not impaired. And basic catalysts.

Specific examples of the basic catalyst used in the present invention are preferably 1-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1,8-diazabicyclo [5.4. 0] -7-undecene and the like, and tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylamine, dimethylbenzylamine and the like. Among them, 1-methyl used in Examples Imidazole is more preferred.

The basic catalyst is preferably contained in an amount of 0 to 0.5 mol with respect to 1 mol of the cationic polymerizable cyclic ether compound having a polymerizable double bond. More preferably, it is 0-0.2 mol.

1-9. In the synthesis of the polymerization inhibitor polyester amic acid (A), as a raw material, other raw materials other than the above may be included as necessary, as long as the purpose of the present invention is not impaired. And polymerization inhibitors.

Specific examples of the polymerization inhibitor used in the present invention include hydroquinone, methylhydroquinone, 4-methoxyphenol, and dibutylhydroxytoluene, and among these, 4-methoxyphenol used in the examples is more preferable.

The polymerization inhibitor is preferably contained in an amount of 0 to 0.1 mol with respect to 1 mol of the cationic polymerizable cyclic ether compound having a polymerizable double bond. More preferably, it is 0-0.05 mol.

1-10. Solvents used in the synthesis reaction of the polyester amic acid (A) Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amic acid (A) include diethylene glycol dimethyl ether and diethylene glycol methyl ethyl ether (hereinafter abbreviated as EDM). ), Diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMEA), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate , Ethyl lactate, 3-methoxybutyl acetate (hereinafter sometimes abbreviated as MBA), and cyclohexanone. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, or diethylene glycol methyl ethyl ether is preferable.

1-11. Method for synthesizing polyester amic acid (A) The polyester amic acid (A) of the present invention is synthesized as follows. In the presence of a solvent, X mole of tetracarboxylic dianhydride, Z mole of polyvalent hydroxy compound, and W mole of cationic polymerizable cyclic ether compound having a polymerizable double bond are reacted to form an intermediate polymer liquid. After obtaining the composition, Y mol of diamine is reacted.

When using a compound having 3 or more acid anhydride groups as a raw material, in the presence of a solvent, a compound having 3 or more mols of tetracarboxylic dianhydride, 3 mols of acid anhydride groups, Z mol After reacting the polyhydric hydroxy compound and the cationic polymerizable cyclic ether compound having a polymerizable double bond of W mole to obtain a liquid composition of an intermediate polymer, Y mole of diamine is reacted.

When a monohydroxy compound is further used as a raw material, it has X moles of tetracarboxylic dianhydride, Z moles of a polyvalent hydroxy compound and a monohydroxy compound, and W moles of a polymerizable double bond in the presence of a solvent. After the cationic polymerizable cyclic ether compound is reacted to obtain a liquid composition of an intermediate polymer, Y mole of diamine is reacted.

When using a compound having three or more acid anhydride groups and a monohydroxy compound as a raw material, in the presence of a solvent, it has three or more mols of tetracarboxylic dianhydride and V mol of acid anhydride groups. After the compound, Z mole polyhydric hydroxy compound and monohydroxy compound, and W mole polymerizable cationic polymerizable cyclic ether compound having a polymerizable double bond were reacted to obtain an intermediate polymer liquid composition, The diamine is reacted.

When synthesizing by the above four methods, the first step for obtaining the intermediate polymer is preferably carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours, and the second step for reacting the intermediate polymer with the diamine is 20 steps. It is good to make it react at -150 degreeC for 0.1 to 6 hours.

Moreover, the polyester amide acid (A) of the present invention may be polymerized as follows. In the presence of a solvent, X moles of tetracarboxylic dianhydride and Z moles of a polyhydroxy compound were reacted to obtain a liquid composition of an intermediate polymer, and then Y moles of diamine were reacted to produce a polyester amic acid. And a cation polymerizable cyclic ether compound having a polymerizable double bond of W mole is reacted therewith.

When using a compound having 3 or more acid anhydride groups as a raw material, in the presence of a solvent, a compound having 3 or more mols of tetracarboxylic dianhydride, 3 mols of acid anhydride groups, Z mol After obtaining a liquid composition of an intermediate polymer by reacting the polyhydric hydroxy compound, a polyester amic acid is obtained by reacting with Y mol of diamine, and there is cationic polymerization with W mol of polymerizable double bond therein. A cyclic ether compound is reacted.

When a monohydroxy compound is further used as a raw material, an intermediate polymer liquid composition is prepared by reacting X mol of tetracarboxylic dianhydride, Z mol of polyhydroxy compound and monohydroxy compound in the presence of a solvent. After obtained, Y mol of diamine is reacted to obtain a polyester amide acid, and W mol of a cationic polymerizable cyclic ether compound having a polymerizable double bond is reacted therewith.

When using a compound having three or more acid anhydride groups and a monohydroxy compound as a raw material, in the presence of a solvent, it has three or more mols of tetracarboxylic dianhydride and V mol of acid anhydride groups. Compound, Z mol polyhydric hydroxy compound and monohydroxy compound are reacted to obtain a liquid composition of an intermediate polymer, then Y mol diamine is reacted to obtain a polyester amide acid, and W mol polymerizability there. A cationically polymerizable cyclic ether compound having a double bond is reacted.

When synthesizing by the above four methods, the first step for obtaining the intermediate polymer is preferably carried out at 40 ° C. to 200 ° C. for 0.2 to 20 hours, and the second step for reacting the intermediate polymer with the diamine is 20 steps. It is better to react at ~ 150 ° C for 0.1 to 6 hours, and the third step of reacting the cationic polymerizable cyclic ether compound having a polymerizable double bond is reacted at 10 to 150 ° C for 0.2 to 20 hours Good.

When the polymerization is performed by the above-described methods, the above basic catalyst or polymerization inhibitor may be added in some cases.

In the case of reacting tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, and cationic polymerizable cyclic ether compound having a polymerizable double bond as raw materials, X, Y, Z, and W are the same between them. It is preferable to set the ratio so that the relations of the expressions (1), (2), and (3) are established. If it is this range, the solubility to the solvent of a polyester amide acid is high, and the applicability | paintability of a photosensitive composition improves.

In the formula (1), 0.2 ≦ Z / Y ≦ 8.0, preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. It is. In the formula (2), 0.2 ≦ (Y + Z) /X≦5.0, preferably 0.5 ≦ (Y + Z) /X≦4.0, and more preferably 0.6 ≦ ( Y + Z) /X≦2.0. Moreover, in Formula (3), it is 0.05 <= W / 2X <= 1.0, Preferably it is 0.1 <= W / 2X <= 0.5.

The same applies to the case where a monohydroxy compound is further used as a raw material.

In the case where tetracarboxylic dianhydride, a compound having 3 or more acid anhydride groups, a diamine, a polyvalent hydroxy compound, and a cationic polymerizable cyclic ether compound having a polymerizable double bond are used as raw materials, X, It is preferable that Y, Z, and W are determined in such a ratio that the relationship of the formula (1), the formula (2), and the formula (3 ′) is established therebetween. If it is this range, the solubility to the solvent of a polyester amide acid is high, and the applicability | paintability of a photosensitive composition improves.

In the formula (1), 0.2 ≦ Z / Y ≦ 8.0, preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. It is. In the formula (2), 0.2 ≦ (Y + Z) /X≦5.0, preferably 0.5 ≦ (Y + Z) /X≦4.0, and more preferably 0.6 ≦ ( Y + Z) /X≦2.0. In the formula (3 ′), 0.05 ≦ W / (2X + rV) ≦ 1.0, preferably 0.1 ≦ W / (2X + rV) ≦ 0.5.

The same applies to the case where a monohydroxy compound is further used as a raw material.

When the reaction solvent is used in an amount of 100 parts by weight or more with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, and cationic polymerizable cyclic ether compound having a polymerizable group, the reaction proceeds smoothly. This is preferable. When a compound having 3 or more acid anhydride groups is used as the essential raw material compound, tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, cationically polymerizable cyclic ether compound having a polymerizable group, and It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total amount of the compound having 3 or more acid anhydride groups. When a monohydroxy compound is further used as the essential raw material compound, the total amount of tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, cationic polymerizable cyclic ether compound having a polymerizable group, and monohydroxy compound is 100 wt. It is preferable to use 100 parts by weight or more of the reaction solvent with respect to parts. In the case where a compound having three or more acid anhydride groups and a monohydroxy compound are used as the essential raw material compound, tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, cationic polymerizable having a polymerizable group It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total amount of the cyclic ether compound, the compound having 3 or more acid anhydride groups and the monohydroxy compound.

The polyester amic acid (A) synthesized using a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound and a cationic polymerizable cyclic ether compound having a polymerizable double bond as raw materials is represented by the formula (4). The structural unit represented by the structural unit represented by Formula (5), and the terminal, the tetracarboxylic dianhydride which is a raw material, diamine, a polyhydric hydroxy compound, and cationic polymerization which has a polymerizable double bond It is constituted by an acid anhydride group, an amino group, a hydroxy group, a polymerizable double bond, a monovalent organic group, or an additive other than these compounds, each derived from a cyclic ether compound. By including such a configuration, curability is improved.

Polyester amide acid (A) synthesized by using tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound, cationic polymerizable cyclic ether compound having a polymerizable double bond, and monohydroxy compound as raw materials, The structural unit represented by Formula (4), the structural unit represented by Formula (5), and the structural unit represented by Formula (6) are included, and the terminal is the above-mentioned acid anhydride group, amino group, hydroxy It is constituted by a group, a polymerizable double bond, a monovalent organic group, a monovalent group derived from a monohydroxy compound, or an additive other than these compounds. By including such a configuration, curability is improved and storage stability of the photosensitive composition is improved as described above.

Polyesteramic acid synthesized using tetracarboxylic dianhydride, compound having 3 or more acid anhydride groups, diamine, polyvalent hydroxy compound, and cationic polymerizable cyclic ether compound having polymerizable double bond as raw materials (A) includes the structural unit represented by the above formula (4) and the structural unit represented by the formula (5), and the terminal has three or more acid anhydride groups and acid anhydride groups described above. It is comprised by the monovalent group derived from the compound to have, an amino group, a hydroxyl group, a polymerizable double bond, or a monovalent organic group, or additives other than these compounds. By including such a configuration, the transparency of the cured film is improved as described above.

It is synthesized using tetracarboxylic dianhydride, a compound having 3 or more acid anhydride groups, a diamine, a polyvalent hydroxy compound, a cationic polymerizable cyclic ether compound having a polymerizable double bond, and a monohydroxy compound as raw materials. The polyester amic acid (A) includes a structural unit represented by the above formula (4), a structural unit represented by the formula (5), and a structural unit represented by the formula (6), The above acid anhydride groups, monovalent groups derived from compounds having 3 or more acid anhydride groups, amino groups, hydroxy groups, polymerizable double bonds, or monovalent organic groups, or additions other than these compounds Composed of things. By including such a configuration, the transparency of the cured film is improved as described above, and the storage stability of the photosensitive composition is improved.

The weight average molecular weight of the obtained polyester amic acid (A) is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in these ranges, flatness and heat resistance are favorable.

The weight average molecular weight in the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). For standard polystyrene, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 of Agilent Technologies) is used, and PLgel MIXED-D (Agilent Technology, Inc.) is used for the column. It can be measured using THF as the mobile phase. The weight average molecular weight of the commercial product in this specification is a catalog publication value.

2. Photosensitive Composition A photosensitive composition according to an embodiment of the present invention includes a polyester amic acid (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), an epoxy compound (D), and Contains additive (E).
2-1. Polyester amide acid having a polymerizable double bond (A)
The polyester amide acid (A) having a polymerizable double bond used in the photosensitive composition is the above-described polyester amide acid (A).

2-2. Compound (B) having a polymerizable double bond
2-2-1. Compound having two or more polymerizable double bonds per molecule Compound (B) having a polymerizable double bond used in the photosensitive composition has a polymerizable double bond other than polyester amic acid (A). A compound. The compound (B) having a polymerizable double bond is not particularly limited except that it is other than the polyester amide acid (A), but is preferably a compound having two or more polymerizable double bonds per molecule.

When the compound (B) having a polymerizable double bond is 50 to 300 parts by weight with respect to 100 parts by weight of the polyester amide acid (A), the residual film ratio after development is improved.

As a compound having two or more polymerizable double bonds per molecule, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin Modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (Meth) acrylate, epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylol Propane tri (meth) acrylate, propylene alcohol Sid-modified trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate , Epichlorohydrin modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate neo Pentyl glycol di (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide modified acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, di Pentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, polybasic acid-modified (meth) acrylic , Allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxyneopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, Ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol (meth) acrylate , Dicyclopentanyl diacrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, polyester pentaacrylate, Reester hexaacrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified diphthalic acid di ( (Meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone Modified tris [(meth) acryloxyethyl] isocyanurate, (meth) acrylated isocyanurate, phen Nyl glycidyl ether acrylate Hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate Toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate Hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate Toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate Isophorone diisocyanate urethane pre Polymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, non-yellowing type oligourethane acrylate, (meth) acrylic acid modified phenol novolac type epoxy resin, cresol novolac type epoxy resin It can be mentioned the (meth) acrylic acid modified product, and carboxylic acid-containing urethane acrylate oligomer.

As the compound having two or more polymerizable double bonds per molecule, the above-mentioned compounds may be used alone, or two or more may be mixed and used.

Among compounds having two or more polymerizable double bonds per molecule, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modification ( Use of a (meth) acrylic oligomer, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, or a mixture thereof is preferable from the viewpoint of heat resistance and chemical resistance of the cured film.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modified (meth) acryl oligomer, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified tri As the acrylate or a mixture thereof, the following commercially available products can be used.

A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; Toagosei Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronics M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 (30-60 wt%), M-452 (25 to 40% by weight) and M-450 (less than 10% by weight) (all trade names; Toagosei Co., Ltd., parentheses content is a catalog of the content of pentaerythritol triacrylate in the mixture) Posted price). Specific examples of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronics M-403 (50-60 wt%), M-400 (40-50 wt%), M-402 (30-40 wt%). , Hereinafter abbreviated as “M-402”), M-404 (30 to 40% by weight), M-406 (25 to 35% by weight), and M-405 (10 to 20% by weight) ( All are trade names; Toagosei Co., Ltd., the content in parentheses is the catalog value of the content of dipentaerythritol pentaacrylate in the mixture). Specific examples of the polybasic acid-modified (meth) acryl oligomer are Aronix M-510 and M-520 (both are trade names; Toagosei Co., Ltd.). A specific example of the isocyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name; Toagosei Co., Ltd.). Specific examples of a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate are Aronix M-313 (30 to 40% by weight) and M-315 (3 to 13% by weight) (both trade names; Toagosei Co., Ltd.) The content in parentheses is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture). A specific example of the acrylic acid-modified product of the phenol novolac type epoxy resin is TEA-100 (trade name; KSM Co., Ltd.). A specific example of the acrylic acid-modified product of the cresol novolac type epoxy resin is CNEA-100 (trade name; KSM Co., Ltd.).

2-2-2. A compound having one polymerizable double bond per molecule and at least one functional group selected from —OH and —COOH per molecule. The photosensitive composition is polymerized from the viewpoint of resolution. A compound having one ionic double bond per molecule and having at least one functional group selected from —OH and —COOH per molecule may be further contained. The compound having one polymerizable double bond per molecule and having at least one functional group selected from —OH and —COOH per molecule is 1 per 100 parts by weight of polyester amic acid (A). When it is ˜50 parts by weight, the resolution is improved.

Examples of the compound having one polymerizable double bond per molecule and at least one functional group of —OH and —COOH per molecule include (meth) acrylic acid, hydroxyethyl ( (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, succinic acid 2- (meth) acryloyloxyethyl, hexahydrophthalic acid 2- ( (Meth) acryloyloxyethyl, phthalic acid 2- (meth) acryloyloxyethyl, phthalic acid 2- (meth) acryloyloxyethyl-2-hydroxyethyl, (meth) acrylic acid 4-hydroxyphenyl, p-hydroxy ( (Meth) acrylanilide, 4-hydroxybutyl (meth) ac Relate, 1,4-cyclohexanedimethanol mono (meth) acrylate, hydroxyethyl (meth) acrylate, glycerin mono (meth) acrylate, acrylic acid 3- (2-hydroxyphenyl), and β-carboxyethyl (meth) acrylate Can be mentioned.

Among these, (meth) acrylic acid 4-hydroxyphenyl and p-hydroxy (meth) acrylanilide have good resolution.

2-3. Photopolymerization initiator (C)
The photopolymerization initiator contained in the photosensitive composition is a polyester amic acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), and an additive. It will not specifically limit if the polymerization of the composition containing an agent (E) can be started.

Examples of the photopolymerization initiator contained in the photosensitive composition include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, Acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-o (Eg, trade name: IRGACURE 907, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (eg, trade name: IRGACURE 369, BASF Japan Ltd.) Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 1 , 2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) (for example, trade name: IRGACURE OXE01, BASF Japan Ltd.), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazole-3 Yl] -1- (O-acetyloxime) (for example, trade name: IRGACURE OXE02, BASF Japan Ltd.), IRGACURE OXE03 (trade name; BASF Japan Ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) (for example, trade name; Adeka Arcles NCI-930, ADEKA Corporation), Adeka Arcles NCI-831 (trade name; ADEKA), Adekaoptomer N-1919 (trade name; ADEKA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (3 ′, 4′-dimethoxystyrene) Ryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2′- Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3 -Bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz Azole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3 -(2-methyl-2-dimethylaminopropionyl) Carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like can be given.

A photoinitiator may be used independently and may mix and use 2 or more. Among the photopolymerization initiators, α-aminoalkylphenone-based, acylphosphine oxide-based, and oxime ester-based photopolymerization initiators are preferable from the viewpoint of the sensitivity of the coating film during exposure and the transparency of the cured film. In this specification, a thin film obtained by pre-drying (pre-baking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing or other methods is referred to as a “coating film”. This coating film is subjected to subsequent steps such as exposure-development-washing-drying, and then becomes a cured film by main baking (post-baking). In the present specification, the thin film in the steps from the preliminary drying to the drying is referred to as “coating film”, for example, “coating film at the time of exposure” or “coating film after development”. Let us indicate whether it is a stage coating.

Among the photopolymerization initiators, 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) or 1,2-propanedione, 1- [4- [4- ( From the viewpoint of the sensitivity of the coating film and the transparency of the cured film, 2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is 20% by weight or more based on the total weight of the photopolymerization initiator. More preferred. Moreover, it is further more preferable in it being 50 weight% or more. The photopolymerization initiator is 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) or 1,2-propanedione, 1- [4- [4- (2- It may consist only of hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime).

2-4. Epoxy compound (D)
The epoxy compound (D) used in the photosensitive composition contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding an epoxy compound (D) to the photosensitive composition of this invention, the heat resistance of a cured film can be improved. When the epoxy compound (D) is 20 to 150 parts by weight with respect to 100 parts by weight of the polyester amide acid (A), the flatness becomes good.

Preferred examples of the epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celoxide 2021P, Daicel Corporation), 1-methyl-4- (2-methyloxy Ranyl) -7-oxabicyclo [4.1.0] heptane (for example, trade name: Celoxide 3000, Daicel Corporation), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4 -[1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2 Mixture with propanol, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane (For example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 1,1,1-tris (4-hydroxyphenyl) ethanetriglycidyl ether (for example, trade name: jER 1032H60, Mitsubishi Chemical Corporation), 1,3 -Bis (oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2-bis (hydroxymethyl)- 1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol (for example, trade name: EHPE3150, DA Cell), jER YX4000, YX4000H, YL6121H (all trade names; Mitsubishi Chemical Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all trade names; Nippon Kayaku Co., Ltd.) Company).

2-5. Ratio of polyester amic acid (A), compound (B) having a polymerizable double bond, photopolymerization initiator (C), and epoxy compound (D) In the photosensitive composition, 100% by weight of polyester amic acid (A) The ratio of the compound (B) having a polymerizable double bond to 20 parts by weight is 20 to 300 parts by weight. When the ratio of the compound (B) having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance and residual film ratio after development is good. The compound (B) having a polymerizable double bond is more preferably in the range of 100 to 300 parts by weight.

In the said photosensitive composition, the ratio of an epoxy compound (D) is 20-200 weight part with respect to 100 weight part of polyester amic acid (A). When the proportion of the epoxy compound (D) is within this range, the balance between heat resistance and flatness is good. More preferably, the epoxy compound (D) is in the range of 20 to 150 parts by weight.

2-6. Additive (E)
Various additives can be added to the photosensitive composition in order to improve coating uniformity, adhesion, transparency, resolution, flatness, and chemical resistance. Additives include anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants, coupling agents such as silane coupling agents, hindered phenols, hindered amines, phosphorus, sulfur Mainly mentioned are antioxidants such as compounds, molecular weight regulators, and epoxy curing agents.

2-6-1. Surfactant A surfactant may be added to the photosensitive composition in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, polyflow KL-245, polyflow no. 75, Polyflow No. 90, polyflow no. 95 (all trade names: Kyoeisha Chemical Co., Ltd.), Disperbeek 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all trade names; Big Chemie Japan) Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all trade names: Shin-Etsu Chemical Co., Ltd.), Surflon-S -101, Surflon-KH-40, Surflon-S611 (all trade names; AGC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, After Gento 601AD, Aftergent 602A, Aftergent 650A, FTX-218 (all trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (All trade names: Mitsubishi Materials Corporation), Megafuck F-171, Megafuck F-177, Megafuck F-410, Megafuck F-430, Megafuck F-444, Gafuck F-472SF, Megafuck F-475, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F -558, Megafuck F-559, Megafuck R-30, Megafuck R-94, Megafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck DS-21 (whichever Product name; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (both trade names, D Kudegusa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxy) Ethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, poly Oxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene Stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene Examples include sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

Among these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surflon-S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, Megafuck F-477, Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkyl At least selected from among carboxylates, fluoroalkylpolyoxyethylene ethers, fluoroalkylsulfonates, fluoroalkyltrimethylammonium salts, and fluoroalkylaminosulfonates Is also preferable because the coating uniformity of the photosensitive composition is increased.

The content of the surfactant in the photosensitive composition is preferably 0.01 to 10% by weight with respect to the total amount of the photosensitive composition.

2-6-2. Coupling agent The photosensitive composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Silaace S510, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Silaace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name: Silaace S810, JNC Corporation), 3-glycidyloxypropyl Silane coupling agents such as trimethoxysilane copolymers (for example, trade name: CoatOSil MP200, Momentive Performance Materials Co., Ltd.), acetoalkoxyaluminum diisopropylate, etc. Aluminum coupling agents, and tetraisopropyl bis (dioctyl phosphite) can be mentioned titanate coupling agents such as titanates.

Among these, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

The content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less with respect to the total amount of the photosensitive composition because adhesion between the formed cured film and the substrate is improved. .

2-6-3. Antioxidant The photosensitive composition may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to high temperatures.

You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the said photosensitive composition. Of these, hindered phenols are preferred from the viewpoint of weather resistance. Specific examples, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (none Product name: BASF Japan Ltd.), ADK STAB AO-20, ADK STAB AO-30, ADK STAB A -50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (trade names; Ltd ADEKA) and the like. Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

The antioxidant is used by adding 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

2-6-4. Molecular Weight Adjusting Agent The photosensitive composition may further contain a molecular weight adjusting agent in order to suppress an increase in molecular weight due to polymerization and to exhibit excellent resolution. Examples of the molecular weight modifier include mercaptans, xanthogens, quinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5-di-t-butylhydroquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid Dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene, and the like.

A molecular weight modifier may be used independently and may be used in combination of 2 or more. Among the molecular weight regulators, naphthoquinone molecular weight regulators are preferred from the standpoint of exhibiting excellent resolution.

Among the molecular weight modifiers, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferable from the viewpoint of resolution. Further, from the viewpoint of resolution, it is preferable that the photopolymerization initiator (C) contains a molecular weight regulator so that the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight regulator. Preferably, the molecular weight modifier is more preferably contained so that the content of the photopolymerization initiator (C) is more than 5.1 times and less than 20 times the content of the molecular weight modifier. It is more preferable to contain the molecular weight regulator so that the content of the photopolymerization initiator (C) is more than 5.2 times the content of the molecular weight regulator and 10 times or less.

2-6-5. Epoxy Curing Agent The photosensitive composition may further contain an epoxy curing agent in order to improve flatness and chemical resistance. Epoxy curing agents include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Although there exist a heat-sensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent is preferable from the viewpoint of avoiding coloring of a cured film and the heat resistance of a cured film.

Specific examples of the acid anhydride curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydrotrimellitic anhydride And aromatic polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride. Among these, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride that can improve the heat resistance of the cured film without impairing the solubility of the photosensitive composition in the solvent are particularly preferable.

Specific examples of the imidazole curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2- a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these, 2-undecylimidazole is particularly preferable because it can improve the curability of the cured film without impairing the solubility of the photosensitive composition in the solvent.

The ratio of the epoxy curing agent to the epoxy compound (D) is 0.1 to 60 parts by weight of the epoxy curing agent with respect to 100 parts by weight of the epoxy compound (D). For example, with respect to the addition amount when the epoxy curing agent is an acid anhydride curing agent, more specifically, the carboxylic anhydride group or carboxyl group in the epoxy curing agent is 0.1 to 1.5 times the epoxy group. It is preferable to add so that it may become equivalent. At this time, the carboxylic acid anhydride group is calculated as divalent. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group so that the equivalent amount of the carboxylic acid anhydride group or the carboxyl group is 0.15 to 0.8 times, since the chemical resistance is further improved.

2-6-6. Ultraviolet Absorber The photosensitive composition may contain an ultraviolet absorber from the viewpoint of further improving the ability to prevent deterioration of the formed patterned transparent film.

Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names, BASF Japan Ltd.).

The ultraviolet absorber is used by adding 0.01 to 10 parts by weight with respect to the total amount of the photosensitive composition.

2-6-7. Anti-aggregation agent The photosensitive composition may contain an anti-agglomeration agent from the viewpoint of blending the solid content with the solvent and preventing aggregation.

Specific examples of the anti-agglomeration agent include Disperbak-145, Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-182, Dispersake-184, Dispersake-185 , Disper Bake-2163, Disper Bake-2164, BYK-220S, Disper Bake-191, Disper Bake-199, Disper Bake-2015 (all trade names: Big Chemie Japan Co., Ltd.), FTX-218, Footent 710FM, They are Footgent 710FS (all trade names, Neos Co., Ltd.), Floren G-600, and Floren G-700 (all trade names, Kyoeisha Chemical Co., Ltd.).

The aggregation inhibitor is used by adding 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

2-6-8. Thermal crosslinking agent The photosensitive composition may contain a thermal crosslinking agent from the viewpoint of further improving heat resistance, chemical resistance, in-film uniformity, flexibility, flexibility, and elasticity.

Specific examples of the thermal crosslinking agent include Nicarak MW-30HM, Nicarak MW-100LM, Nicarak MW-270, Nicarak MW-280, Nicarac MW-290, Nicarac MW-390, Nicarac MW-750LM (all trade names; Sanwa Chemical Co., Ltd.).

The thermal crosslinking agent is used by adding 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

2-6-9. Photoacid generator The photosensitive composition may contain a photoacid generator from the viewpoint of improving resolution. A 1,2-quinonediazide compound is used as the photoacid generator.

Specific examples of 1,2-quinonediazide compounds 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-sulfone Acid esters;
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-naphtho Quinonediazide-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-hydroxyphenyl) 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, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester;
Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-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-hydroxyphenyl) -2-hydroxy Phenylmethane-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 Sulfonate esters;
2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, and 2,2,4-trimethyl-7,2 ′, 4′- Trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester.

The photoacid generator is used in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

式（７）において、Ｒ^６は水素またはメチルであり、Ｒ^７〜Ｒ^１０は炭素数１〜５のアルキルであり、Ｒ^１１は炭素数１〜１０のアルキルであり、ｍは１〜１０の整数であり、ｎは１〜１５０の整数である。 2-6-10. Other additives The photosensitive composition comprises at least one of a radically polymerizable compound (P1) represented by the following formula (7), a radically polymerizable compound (P2) having alkoxysilyl, and epoxy, carboxyl and hydroxyphenyl. The polymer may further contain a polymer obtained by radical copolymerization of a radically polymerizable compound (P3) having one (hereinafter also referred to as “radical copolymerization polymer”).

In Formula (7), R ⁶ is hydrogen or methyl, R ^{7 to} R ¹⁰ are alkyl having 1 to 5 carbons, R ¹¹ is alkyl having 1 to 10 carbons, and m is 1 to 10 It is an integer, and n is an integer of 1 to 150.

2-6-10-1. Radical polymerizable compound (P1)
Since the radically polymerizable compound (P1) represented by the formula (7) acts as a surfactant, the radical copolymer polymer acts as a surfactant by using (P1) as a raw material. Even if a surfactant is not added separately, the flatness, adhesion to the base substrate, and coatability are improved. By adding the radically polymerizable compound (P1), the radical copolymerized polymer is easily revealed on the film surface.

In the photosensitive composition, in the radical polymerizable compound (P1) represented by the formula (7), R ⁶ is hydrogen or methyl, R ^{7 to} R ¹⁰ are methyl, R ¹¹ is alkyl having 1 to 10 carbons, The compound whose m is an integer of 1-5 and n is an integer of 1-150 is preferable. R ⁶ is methyl, R ^{7 to} R ¹⁰ are methyl, R ¹¹ is butyl, m is 3, and n is an integer of 1 to 150, and n is more preferably an integer of 30 to 70. , N is preferably an integer of 50 to 70. The weight average molecular weight of the radically polymerizable compound (P1) represented by the formula (7) is preferably 500 to 8000.

The radically polymerizable compound (P1) can be produced by a known method. A commercially available product may also be used. For example, FM-0711, FM-0721, FM-0725 (all are brand names; JNC Corporation) etc. are mentioned.

2-6-10-2. Radical polymerizable compound having alkoxysilyl (P2)
In the photosensitive composition, a radical polymerizable compound (P2) having alkoxysilyl is used as a raw material for obtaining the radical copolymer. Preferred radical polymerizable compounds (P2) are 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) ) One or more selected from the group consisting of acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane. Among these, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane are preferable because of good flatness. By using (P2), transparency, chemical resistance and the like are improved. Moreover, adhesiveness with a base material improves by the silane coupling effect.

2-6-10-3. Radical polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl (P3)
In the photosensitive composition, a radical polymerizable compound (P3) having at least one of epoxy, carboxyl, and hydroxyphenyl is used as a raw material for obtaining the radical copolymer. The preferred radically polymerizable compound (P3) is at least one selected from the group consisting of glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid, and 4-hydroxyphenyl vinyl ketone. . (P3) functions as a crosslinking agent for the polymer and contributes to improvement in heat resistance, chemical resistance, and the like.

2-6-10-4. Method for Producing Radical Copolymer A radical copolymer is a radical polymerizable compound (P1) represented by formula (7), a radical polymerizable compound (P2) having alkoxysilyl, and at least epoxy, carboxyl, and hydroxyphenyl. It is obtained by radical copolymerizing a radically polymerizable compound (P3) having one. The method for producing the radical copolymer is not particularly limited, but the radical copolymer can be produced by heating the radical polymerizable compounds in the presence of a radical initiator. As the radical initiator, organic peroxides, azo compounds and the like can be used. Although the reaction temperature of radical copolymerization is not specifically limited, Usually, it is the range of 50 to 150 degreeC. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. In addition, the reaction can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

The solvent used for the above radical copolymerization reaction is preferably a solvent in which the polymer to be produced dissolves. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3 -Methyl oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2- Propyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropyl Methyl pionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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, and diethylene glycol methyl ethyl ether,. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

The radical copolymer used in the photosensitive composition may be a radical copolymer solution in consideration of handling properties while leaving the solvent used in the polymerization as it is. The solid radical copolymer may be used.

A radical copolymer having a weight average molecular weight in the range of 1,000 to 50,000 determined by GPC analysis using polystyrene as a standard is preferable because of good film formability. Furthermore, when the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is good and more preferable. Furthermore, when the weight average molecular weight is in the range of 2,500 to 15,000, the flatness and chemical resistance of the cured film are good, which is particularly preferable.

Other additives are used by adding 0.1 to 20 parts by weight based on the total amount of the photosensitive composition.

2-7. Solvent A solvent may be added to the photosensitive composition. Solvents optionally added to the photosensitive composition of the present invention include polyester amic acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), and the like. Solvents that can be dissolved are preferred. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, 3 -Methyl oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2- Propyl hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropyl Methyl pionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, aceto Methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 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, and diethylene glycol methyl ethyl ether. The solvent may be one of these, or a mixture of two or more of these.

2-8. Storage of Photosensitive Composition When the photosensitive composition is stored in the range of −30 ° C. to 25 ° C., the temporal stability of the composition becomes good. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

3. Cured film of photosensitive composition The photosensitive composition comprises a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), and an additive. It can be obtained by mixing (E), further selecting and adding a solvent if necessary, and mixing and dissolving them uniformly. As the additive (E), a coupling agent, a surfactant, and other additives can be selected and used as necessary depending on the intended properties.

The photosensitive composition prepared as described above (after dissolving in a solvent in the case of a solid state without a solvent) is applied to the substrate surface, and the film is formed by removing the solvent, for example, by heating. be able to. Conventionally known methods such as spin coating, roll coating, dipping, flexo, spray, and slit coating can be used to apply the photosensitive composition to the substrate surface. Next, this coating film is heated (prebaked) with a hot plate, an oven or the like. The heating conditions vary depending on the type and mixing ratio of each component, but are usually 70 to 150 ° C., 5 to 15 minutes for an oven, and 1 to 5 minutes for a hot plate.

Thereafter, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet irradiation is suitably 5 to 1000 mJ / cm ^{2 in} i-line. The photosensitive composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and becomes insoluble in an alkali developer.

Next, the coating film is immersed in an alkaline developer by shower development, spray development, paddle development, dip development, etc., and unnecessary portions are dissolved and removed. Specific examples of the alkali developer include aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, surfactant or the like can be added to the alkaline developer.

Finally, in order to completely cure the coating film, a cured film can be obtained by heat treatment at 180 to 250 ° C., preferably 200 to 250 ° C., for 30 to 90 minutes for an oven and 5 to 30 minutes for a hot plate. .

In the cured film thus obtained, when heated, 1) the polyamic acid portion of the polyester amic acid (A) is dehydrated to form an imide bond, and 2) the carboxyl group of the polyester amic acid (A) is Since it has a high molecular weight by reacting with an epoxy compound, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element and a solid-state imaging element can be manufactured using the color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film, in addition to a protective film for a color filter. . Furthermore, the cured film of the present invention is effective even when used as a protective film for LED light emitters.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples.

[Synthesis Example 1] Synthesis of polyesteramide acid (A1) having polymerizable double bond In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butanetetra Carboxylic dianhydride (BT-100), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Chemical Co., Ltd.), benzyl alcohol, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE) in the following order. And stirred for 6 hours at 125 ° C. in a dry nitrogen stream (synthesis first step).
PGMEA 43.10g
BT-100 2.52g
SMA1000P 12.01g
Benzyl alcohol 3.67g
4HBAGE 4.24g

Thereafter, the solution after the reaction was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (DDS) and PGMEA were added in the following weights, stirred at 20 to 30 ° C. for 2 hours, and then at 125 ° C. for 1 hour. Stirring (synthesis second step).
DDS 0.79g
PGMEA 6.74g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.25]

The solution was cooled to room temperature to obtain a 30% by weight solution (A1) of a pale yellow transparent polyester amide acid. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A1) was 32,300.

[Synthesis Examples 2 to 7] Synthesis of Polyester Amic Acid Solution (A2 to A7) According to the method of Example 1, each component was reacted with the weight (unit: g), temperature and time shown in Table 1 to obtain polyester. Amic acid solutions (A2) to (A7) were obtained.

In addition, about the name in Table 1, PGMEA is propylene glycol monomethyl ether acetate, ODPA is 4,4'- diphenyl ether tetracarboxylic dianhydride, GMA is glycidyl methacrylate, OXE-30 is (3-ethyloxetane-3-yl. ) Each represents methyl methacrylate.

[Synthesis Example 8] Synthesis of polyesteramide acid (A8) having polymerizable double bond In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butanetetra Carboxylic dianhydride (BT-100), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Chemical Co., Ltd.), and benzyl alcohol were charged in the following weights in this order. Stir for hours (synthesis first step).
PGMEA 26.74g
BT-100 1.91g
SMA1000P 9.12g
Benzyl alcohol 2.79g

Thereafter, the solution after the reaction was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (DDS) and PGMEA were added in the following weights, stirred at 20 to 30 ° C. for 2 hours, and then at 125 ° C. for 1 hour. Stirring (synthesis second step).
DDS 0.60g
PGMEA 4.41g

Thereafter, the solution after the reaction was cooled to 25 ° C., glycidyl methacrylate (GMA), 1-methylimidazole (NMI), and 4-methoxyphenol (MQ) were added in the following weights and stirred at 80 ° C. for 8 hours ( Synthesis third step).
GMA 0.51g
NMI 0.056g
MQ 0.011g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.06]

The solution was cooled to room temperature to obtain a 30% by weight solution (A8) of a pale yellow transparent polyester amide acid. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A8) was 14,700.

[Synthesis Examples 9 to 11] Synthesis of Polyester Amic Acid Solution (A9 to A11) According to the method of Example 8, each component was reacted at the weight (unit: g), temperature and time described in Table 2 to obtain polyester. Amic acid solutions (A9) to (A11) were obtained.

[Comparative Synthesis Examples 1 and 2] Synthesis of polyester amic acid solution (a1 and a2) According to the method of Example 1, each component was reacted at the weight (unit: g), temperature and time described in Table 3, Polyester amide acid solutions (a1) and (a2) were obtained.

[Comparative Synthesis Example 3] Synthesis of polyester amic acid solution (a3) In a four-necked flask equipped with a stirrer, dehydrated and purified propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butanetetracarboxylic dianhydride (BT-100), SMA1000P (trade name; styrene / maleic anhydride copolymer, Kawa Crude Chemical Co., Ltd.), benzyl alcohol, glycidyl methacrylate (GMA), 3,3′-diaminodiphenylsulfone (DDS) in this order. And stirred at 125 ° C. for 2 hours under a dry nitrogen stream.
PGMEA 49.85g
BT-100 2.66g
SMA1000P 12.66g
Benzyl alcohol 3.87g
GMA 3.18g
DDS 0.83g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.25]

A white insoluble matter was generated, and a uniform solution could not be obtained.

[Comparative Synthesis Example 4] Synthesis of Polyesteramide Acid Solution (a4) According to the method of Comparative Example 3, each component was reacted with the weight (unit: g), temperature and time shown in Table 4, but polyesteramide A homogeneous solution of acid could not be obtained.

[Example 1]
A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and the polyester amic acid solution (A1) (polyester amic acid (A) component) obtained in Synthesis Example 1 and U-6LPA (Shin Nakamura Chemical) were added to the flask. Kogyo Co., Ltd.) (compound (B) component having a polymerizable double bond), NCI-930 (ADEKA) (photopolymerization initiator (C) component), VG3101L (epoxy compound (D) component), Trimerit Acid anhydride (TMA), 3-glycidoxypropyltrimethoxysilane (for example, trade name: Silaace S510, JNC Corporation), AO-60 (ADEKA Corporation), Kinoexter QE-3124 (Kawasaki Chemical Industry Co., Ltd.) ) (Additive (E) component), and dehydrated and purified PGMEA and EDM in the weight (unit: g) shown in Table 5-1. Inclusive, stirred for 3 hours at room temperature, and uniformly dissolved therein. Subsequently, BYK-342 (BYK Additives & Instruments) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to prepare a photosensitive composition.

[Examples 2 to 11]
According to the method of Example 1, each component was mixed with the weight (unit: g) described in Tables 5-1 and 5-2 to obtain a photosensitive composition.

表中、「Ｍ−４０２」はジペンタエリスリトールペンタアクリレート及びジペンタエリスリトールヘキサアクリレートの混合物；アロニックス Ｍ−４０２（東亞合成株式会社）、「ＲＳ−７２−Ｋ」は界面活性剤；メガファックＲＳ−７２−Ｋ（ＤＩＣ株式会社）を表す（以下同じ）。

In the table, “M-402” is a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; Aronix M-402 (Toagosei Co., Ltd.), “RS-72-K” is a surfactant; Represents 72-K (DIC Corporation).

表中の「Ｍ−５２０」は多塩基酸変性（メタ）アクリルオリゴマー；アロニックス Ｍ−５２０（東亞合成株式会社）、「ＥＨＰＥ３１５０」は２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物；ＥＨＰＥ３１５０（株式会社ダイセル）、「Ｆ−５５６」は界面活性剤；メガファックＦ−５５６（ＤＩＣ株式会社）を表す。

“M-520” in the table is a polybasic acid-modified (meth) acrylic oligomer; Aronix M-520 (Toagosei Co., Ltd.), “EHPE3150” is 1,2-bis (hydroxymethyl) -1-butanol 2-Epoxy-4- (2-oxiranyl) cyclohexane adduct; EHPE3150 (Daicel Corporation), “F-556” represents a surfactant; Megafac F-556 (DIC Corporation).

These photosensitive compositions were spin-coated on a glass substrate at 950 rpm for 10 seconds, and prebaked on a 100 ° C. hot plate for 80 seconds. Next, exposure was performed with an exposure gap of 100 μm using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) through a mask having a hole and line pattern with a width of 50 μm in the air. The exposure dose was 30 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name; Ushio Electric Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio Electric Co., Ltd.). The coated film after exposure was developed with NaHCO ₃ aqueous solution at 27 ° C. for 40 seconds, and then the coated film was washed with running water (pure water) for 20 seconds. Furthermore, it post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a patterned cured film with a film thickness of 1.5 micrometers.

The cured film thus obtained was evaluated for the remaining film ratio and resolution after development by the following methods. The results are shown in Table 6-1 and Table 6-2.

[Evaluation method of residual film ratio after development]
Using a step / surface roughness / fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.), the film thickness before development and the film thickness after development are measured, and the remaining film ratio after development (film after development) (Thickness × 100 / film thickness before development)) was calculated. The case where the remaining film ratio after development was 80% or more was marked with ◎, the case where it was 75% or more was marked with ◯, and the case where the remaining film ratio after development was less than 75% was marked with ×.

Here, before development means “after pre-baking”, and after development means “after washing and drying”.

[Resolution evaluation method]
The obtained glass substrate with a patterned transparent body was observed with a 1,000 times optical microscope, and the resolution of a 20 μm hole pattern was confirmed. The case where the image was resolved was marked with “◯”, and the case where there was a residue and was not resolved was marked with “x”.

[Comparative Examples 1-4]
According to the method of Example 1, each component was mixed and dissolved with the weight (unit: g) shown in Table 7 to obtain a photosensitive composition.

About the cured film obtained according to the method of the Example, the post-development residual film rate and the resolution were evaluated according to the Example. The results are shown in Table 8.

As is clear from the results shown in Table 6-1 and Table 6-2, a cured film using the photosensitive composition containing the polyester amide acid (A) having a polymerizable double bond of Examples 1 to 11 was used. It can be seen that the remaining film ratio after development and the resolution are balanced. On the other hand, as shown in Table 8, the cured films using the photosensitive compositions containing the polyester amide acids of Comparative Examples 1 to 4 are all inferior in the residual film ratio after development.

As described above, a polymerizable double, which is a reaction product from a raw material containing a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a cationic polymerizable cyclic ether compound having a polymerizable double bond as an essential component. By using the polyester amic acid (A) having a bond, it was possible to satisfy the remaining film ratio and resolution after development.

The cured film obtained from the photosensitive composition of the present invention has excellent properties as an optical material such as heat resistance, transparency, flatness, resolution, and remaining film ratio, so color filters, LED light emitting elements, It can also be used as a protective film for a light receiving element or the like and as a transparent insulating film formed between a TFT and a transparent electrode or between a transparent electrode and an alignment film.

Claims (12)

A reaction product from a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond;
In the raw material, X mole of tetracarboxylic dianhydride, Y mole of diamine, Z mole of polyvalent hydroxy compound and W mole of cationic polymerizable cyclic ether compound having a polymerizable double bond are represented by the following formula (1). ), A polyester amic acid (A), which is contained at a ratio such that the relationship of formula (2) and formula (3) is established;

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / 2X ≦ 1.0 (3) A reaction product from the raw material further comprising a compound having three or more acid anhydride groups,
In the raw material, X mol of tetracarboxylic dianhydride, Y mol of diamine, Z mol of polyhydroxy compound, W mol of cationic polymerizable cyclic ether compound having a polymerizable double bond, and V mol of acid anhydride The polyester amide acid (A) according to claim 1, comprising a compound having 3 or more groups at a ratio such that the relationship of the following formula (1), formula (2) and formula (3 ') is satisfied;

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)
0.05 ≦ W / (2X + rV) ≦ 1.0 (3 ′)

The compound having 3 or more acid anhydride groups contains r acid anhydride groups per molecule, and is 0.1% with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound. Use ~ 500 parts by weight. The polyester amide acid (A) according to claim 1 or 2, comprising a structural unit represented by the following formula (4) and a structural unit represented by the formula (5);

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, R ⁵ is independently H or a group having a polymerizable double bond, and
R ⁵ in the polyester amic acid (A) is not all H. The polyester amic acid (A) according to claim 1 or 2, further comprising a monohydroxy compound in the raw material. The polyester amide acid (A) according to claim 4, comprising a structural unit represented by the following formula (4), a structural unit represented by the formula (5), and a structural unit represented by the formula (6);

In the above formula, R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, R ² is a residue obtained by removing two —NH ₂ from diamine, and R ^{2 3} is a residue obtained by removing two —OH from a polyvalent hydroxy compound, R ⁴ is a residue obtained by removing —OH from a monohydroxy compound, and R ⁵ independently represents H or a polymerizable double bond. A group having and
R ⁵ in the polyester amic acid (A) is not all H. The cationic polymerizable cyclic ether compound having a polymerizable double bond has a (meth) acryloxy group, and
The polyester amide acid (A) according to claim 1, 2 or 4, which has a glycidyl group or an oxetanyl group. The cationic polymerizable cyclic ether compound having a polymerizable double bond is glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxy. Butyl acrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate,
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- Acrylic esters such as (2-acryloyloxyethyl) oxetane and 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3 -D It is at least one chosen from the group consisting of Ruokisetan, polyester amide acid of claim 1, 2 or 4 (A). The tetracarboxylic dianhydride includes 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) At least one compound selected,
The diamine is at least one of 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;
The polyvalent hydroxy compound includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, 2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, tris (2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) The polyester amide acid (A) according to claim 1, 2 or 4, which is at least one selected from the group consisting of ethanol. The polyester amide acid (A) according to claim 2 or 4, wherein the compound having 3 or more acid anhydride groups is a styrene-maleic anhydride copolymer. The polyester monoamic acid according to claim 4, wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. A). The polyester amide acid (A) of any one of Claims 1-10, the compound (B) which has a polymerizable double bond, a photoinitiator (C), an epoxy compound (D), and an additive ( A photosensitive composition comprising E). The photosensitive composition of Claim 11 whose weight average molecular weights of the said polyester amide acid (A) are 1,000-200,000.