TW201809872A - Photosensitive compositions and cured film having excellent linearity in linear patterning without ripples in a process of development - Google Patents

Abstract

The present invention relates to photosensitive compositions for a protective film having good heat resistance and excellent linearity in linear patterning in a short time of development, and a cured film obtained from the photosensitive composition. The photosensitive composition of the present invention comprises a polyester proline (A), an epoxy group-containing copolymer (B), and a 1,2-quinone diazide compound (C). The said polyester proline acid (A) includes a constituent unit represented by formula (1) and a constituent unit represented by formula (2). The said epoxy group-containing copolymer (B) is a copolymer of polymerizable compounds (b1) and polymerizable compounds (b2) other than (b1), and the polymerizable compound (b2) includes a polymerizable compound having a phenolic hydroxyl group.

Description

Photosensitive composition and cured film

The present invention relates to the formation of an insulating material in electronic parts, a passivation film, a buffer coating film, an interlayer insulating film or a planarizing film in a semiconductor device, or an interlayer insulating film or a protective film for a color filter in a display element. A photosensitive composition used in the above, a cured film using the photosensitive composition, and an electronic component having the cured film.

When a protective film is formed only in a required portion or a hole pattern is formed in an insulating film, a photosensitive composition has been used. Examples of the photosensitive composition include an acrylic positive photosensitive composition (Patent Document 1). With the improvement of the required characteristics of the reliability required for a display and the improvement of the heat resistance required for a display member, the material described in Patent Document 1 has a problem in that it has a higher heat resistance. In order to solve this problem, a polyester melamine type positive photosensitive composition having good heat resistance has been proposed (Patent Document 2). In order to cope with the lower price of displays in recent years, it is necessary to increase the number of manufacturing units per unit time and shorten the time of each step. Among them, in the positive-type photosensitive composition described in Patent Document 2, when the development time is short, a problem arises that the shape of the line pattern cannot be linear and becomes corrugated. If the line pattern is corrugated, the display quality of the panel is reduced. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 5-165214 [Patent Document 2] Japanese Patent Laid-Open No. 2008-102351

[Problems to be Solved by the Invention] A problem of the present invention is to provide a photosensitive composition for a protective film or insulation having good heat resistance and good linearity of the line pattern shape during short-term development. [Means for solving problems]

The inventors of the present invention conducted diligent research in order to solve the problems, and as a result, they found that the object can be achieved by the following composition and a cured film obtained by curing the composition, and have completed the present invention. The product includes polyester amidate, an epoxy-containing copolymer, and a 1,2-quinonediazide compound. The present invention includes the following configurations.

[1] A photosensitive composition comprising: a polyester phosphonium acid (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C); the polyester fluorene The amino acid (A) includes a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2); the epoxy-group-containing copolymer (B) is polymerizable having an epoxy group A copolymer of a polymerizable compound (b2) other than the compounds (b1) and (b1); the polymerizable compound (b2) includes a polymerizable compound having a phenolic hydroxyl group, In formula (1), R ¹ is an organic group having 2 to 1000 carbons, and R ² is an organic group having 2 to 1000 carbons; In formula (2), R ³ is an organic group having 2 to 1000 carbons, and R ⁴ is an organic group having 2 to 100 carbons.

[2] The photosensitive composition according to item [1], wherein the structural unit represented by the formula (1) is a compound (a1) and a diamine (a2) having two or more acid anhydride groups as A structural unit of a raw material; The structural unit represented by the said Formula (2) is a structural unit which used the compound (a1) which has two or more acid anhydride groups, and a polyhydroxy compound (a3) as a raw material.

[3] The photosensitive composition according to item [2], wherein the compound (a1) having two or more acid anhydride groups is selected from a tetracarboxylic dianhydride and a styrene-maleic anhydride copolymer One or more compounds of the above; the polyester amidate (A) is a tetracarboxylic dianhydride containing X mole, and Y in a ratio that satisfies the relationship of the following formula (3) and formula (4): The reaction product of Mohr's diamine and Z Moll's polyhydroxy compound is 0.2 ≦ Z / Y ≦ 8.0 (3) 0.2 ≦ (Y + Z) /X≦5.0 (4).

[4] The photosensitive composition according to item [1], wherein the polymerizable compound (b1) having an epoxy group is one or more selected from (meth) acrylates having an epoxy group; The polymerizable compound of a phenolic hydroxyl group is one or more selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6), In formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbons, R ⁶ is a single bond or -C (= O)-, and R ⁷ to R ¹¹ are each independently a hydroxyl group or a carbon number 1 to An organic group of 7, wherein at least one of R ⁷ to R ¹¹ is a hydroxyl group; In formula (6), R ¹² is hydrogen or an organic group having 1 to 7 carbon atoms, R ¹³ is -O- or -NH-, and R ¹⁴ is a single bond or a divalent organic group having 1 to 40 carbon atoms, R ¹⁵ to R ¹⁹ are each independently a hydroxyl group or an organic group having 1 to 7 carbon atoms, and at least one of R ¹⁵ to R ¹⁹ is a hydroxyl group.

[5] The photosensitive composition according to item [4], wherein the (meth) acrylate having an epoxy group is glycidyl (meth) acrylate; a compound represented by the formula (5) Is one or more selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenylvinyl ketone; the compound represented by the formula (6) is selected from (meth) acrylic 4- One or more of hydroxyphenyl ester, 4-hydroxyphenyl (meth) acrylamide, and 4-hydroxyphenyloxyethyl (meth) acrylate.

[6] The photosensitive composition according to item [1], wherein the epoxy group-containing copolymer is copolymerized with 100% by weight of the total amount of the polyester amidate (A) and the epoxy group-containing copolymer (B). The content of the substance (B) is 20% by weight to 90% by weight, and 1,2-quinone is 100 parts by weight based on 100 parts by weight of the total amount of the polyester amidate (A) and the epoxy group-containing copolymer (B). The diazide compound (C) is 5 to 40 parts by weight.

[7] A cured film obtained from the photosensitive composition according to any one of the items [1] to [6]. [Effect of the invention]

The photosensitive composition according to a preferred embodiment of the present invention is a material having good heat resistance and good linearity in the shape of a line pattern when developed in a short time. When used as a color filter protective film for a color display element, the photosensitive composition can be improved. Reliability and display quality, and can improve productivity in the manufacture of color filter protective films. It can also be used as a protective film and an insulating film for various optical materials.

In this specification, in order to show one or both of "acrylic acid" and "methacrylic acid", it may be expressed as "(meth) acrylic acid". Similarly, in order to indicate one or both of "acrylate" and "methacrylate", it is sometimes expressed as "(meth) acrylate", and to indicate "acrylamide" and "methacrylamide" "One or both" is sometimes expressed as "(meth) acrylamide". In order to indicate one or both of "acryloxy" and "methacryloxy", it is sometimes expressed as "(Meth) acryloxy".

<1. Photosensitive composition> The photosensitive composition of the present invention is a polyester amine acid (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C).组合 物。 Composition.

Regarding preferred composition ratios of the polyester amidate (A), the epoxy group-containing copolymer (B), and the 1,2-quinonediazide compound (C), the polyester amidate (A) and the ring-containing The content of the epoxy-containing copolymer (B) is 20% to 90% by weight based on 100% by weight of the total amount of the oxygen-containing copolymer (B). The total amount of the epoxy group-containing copolymer (B) is 100 parts by weight, and the 1,2-quinonediazide compound (C) is 5 to 40 parts by weight.

In addition, the photosensitive composition of the present invention may further include components other than those described above within a range in which the effects of the present invention are obtained.

<1-1. Polyester Amidate (A)> The polyester amidate (A) has a structural unit represented by the formula (1) and a structural unit represented by the formula (2).

The polyester amido acid (A) can be obtained by reacting a compound (a1) having two or more acid anhydride groups, a diamine (a2), and a polyhydroxy compound (a3) as essential components. In this case, in Formulas (1) and (2), R ¹ and R ³ are residues obtained by removing two -CO-O-CO- from the compound (a1) having two or more acid anhydride groups. R ² is a residue obtained by removing two -NH ₂ from a diamine (a2), and R ⁴ is a residue obtained by removing two -OH from a polyhydroxy compound (a3).

At least a solvent is required for the synthesis of polyester amidate (A). This solvent can be left as it is, and a liquid or gel-like polyester glutamic acid solution in consideration of handling properties can be used to produce a photosensitive composition. The solvent can also be removed and a solid in consideration of handling properties can be used. Polyester amidate to form a photosensitive composition.

Further, in the synthesis of the polyester amidate (A), other compounds than those described above may be included within a range that does not impair the object of the present invention. Examples of other raw materials include monohydroxy compounds and monoamines having an alkoxysilyl group.

<1-1-1. Compound (a1) having two or more acid anhydride groups> In the present invention, as a raw material for obtaining polyester amido acid (A), a compound having two or more acid anhydride groups ( a1).

Examples of preferred compounds of the compound (a1) having two or more acid anhydride groups include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and maleic acid. Copolymers of oxalic anhydride and other compounds.

Specific examples of the compound (a1) having two or more acid anhydride groups are preferably the compounds used in the examples, and examples thereof include 3,3 ', 4,4'- as an aromatic tetracarboxylic dianhydride. Diphenyl ether tetracarboxylic dianhydride (3,3 ', 4,4'-diphenylether tetracarboxylic dianhydride, hereinafter abbreviated as "ODPA"), and 1,2,3,4- as aliphatic tetracarboxylic dianhydride Butanetetracarboxylic dianhydride (hereinafter abbreviated as "BT-100") and a styrene-maleic anhydride copolymer which is a copolymer of maleic anhydride and other compounds.

In addition, as a specific example of the compound (a1) having two or more acid anhydride groups, in addition to the compounds described above, 3,3 ', 4,4'-dibenzoyl, which is an aromatic tetracarboxylic dianhydride, may be mentioned. Ketone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylphosphonium tetracarboxylic dianhydride, 2,2', 3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl碸 tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2 -[Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride and ethylene glycol bis (anhydrotrimellitate); cyclobutane tetracarboxylic acid bis as an alicyclic tetracarboxylic dianhydride Anhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride as an aliphatic tetracarboxylic dianhydride. At least one of the specific examples of the compound (a1) having the two or more acid anhydride groups is used.

In specific examples of these compounds (a1) having two or more acid anhydride groups, it is easy to obtain and provide polyester amidate (A) having good compatibility with the epoxy group-containing copolymer (B). The compound is more preferably 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, ODPA, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, BT-100, ethylene glycol bis (anhydrotrimellitic acid ester) and styrene-maleic anhydride copolymer, particularly preferably 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride , ODPA, BT-100 and styrene-maleic anhydride copolymer.

In addition, as a specific example of a commercially available styrene-maleic anhydride copolymer, SMA3000P (Molar ratio of styrene / maleic anhydride: 3, weight average molecular weight 9,500, number average molecular weight 3,800) SMA2000P (Molar ratio of styrene / maleic anhydride: 2, weight average molecular weight 7,500, number average molecular weight 3,000) and SMA1000P (Molar ratio of styrene / maleic anhydride: 1, weight average molecular weight 5,500 , Number average molecular weight 2,000) (both trade names; Sichuan Crude Chemical Co., Ltd., the values recorded in the catalog). If calculated based on the molar ratio and number average molecular weight of styrene / maleic anhydride in the catalog, the average carbon number per molecule of SMA3000P is 330, the average carbon number per molecule of SMA2000P is 240, and the average carbon number of SMA1000P per The average carbon number of a molecule is 120.

<1-1-2. Diamine (a2)> In the present invention, a diamine (a2) is used as a raw material for obtaining polyester amidate (A).

Examples of preferred compounds of the diamine (a2) include a diamine having two benzene rings and a diamine having four benzene rings.

Specific examples of the diamine (a2) are preferably the compounds used in the examples, and examples thereof include 3,3'-diaminodiphenylphosphonium (3,3'- diamino diphenyl sulfone (hereinafter abbreviated as "DDS").

In addition, as specific examples of the diamine (a2), in addition to the compound, 4,4'-diaminodiphenylsulfonium and 3,4 'as diamines having two benzene rings may be mentioned. -Diaminodiphenylfluorene; and bis [4- (4-aminophenoxy) phenyl] fluorene, a bis [4- (3-aminophenoxy group) as a diamine having four benzene rings ) Phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl] fluorene, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy ) Phenyl] fluorene, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] fluorene, and 2,2-bis [4- (4-amine Phenylphenoxy) phenyl] hexafluoropropane, at least one of the specific examples of the diamine (a2) can be used.

Among the specific examples of these diamines (a2), as the compound which is easily available and provides a polyester amido acid (A) having good compatibility with the epoxy group-containing copolymer (B), DDS and Bis [4- (3-aminophenoxy) phenyl] fluorene is particularly preferably DDS.

<1-1-3. Polyhydroxy compound (a3)> In the present invention, a polyhydroxy compound (a3) is used as a raw material for obtaining polyester amidate (A).

Examples of preferred compounds of the polyhydroxy compound (a3) include aliphatic diols, compounds represented by the following formula (H-1), compounds represented by the following formula (H-2), Polyols of cyanuric ring. In formula (H-1), R ¹⁰¹ is a single bond or an organic group having 1 to 10 carbon atoms; In Formula (H-2), R ¹⁰² is an organic group having 1 to 10 carbon atoms.

Specific examples of the polyhydroxy compound (a3) are preferably those used in the examples, and 1,4-butanediol, which is an aliphatic diol, may be mentioned.

In addition, as specific examples of the polyhydroxy compound (a3), in addition to the compound, ethylene glycol, propylene glycol, 1,5-pentanediol, and 1,6-hexanediethylene as aliphatic diols can also be mentioned. Alcohol, 1,7-heptanediol, and 1,8-octanediol; 2,2-bis (4-hydroxycyclohexyl) propane and 4,4'-dioxane as compounds represented by formula (H-1) Hydroxydicyclohexyl; 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) ethanol as compounds represented by formula (H-2); and polyhydric alcohols having an isocyanuric ring As the tris (2-hydroxyethyl) isocyanurate, at least one of the specific examples of the polyhydroxy compound (a3) can be used.

Among specific examples of these polyhydric hydroxy compounds (a3), 1 is more preferred as a compound that is easily available and provides a polyester amido acid (A) having good compatibility with the epoxy group-containing copolymer (B). 1,4-butanediol and 1,6-hexanediol, and 1,4-butanediol is particularly preferable.

<1-1-4. Monohydroxy compounds> Among the raw materials of polyester phosphoamic acid (A), other raw materials other than those mentioned above may be included as necessary, as long as the object of the present invention is not impaired. Examples of the raw material include a monohydroxy compound.

Examples of preferred compounds of the monohydroxy compound include an aliphatic monohydric alcohol, a compound represented by the following formula (H-3), an alicyclic monohydric alcohol, and an aromatic monohydric alcohol. In the formula (H-3), R ¹⁰³ to R ¹⁰⁶ are each independently hydrogen or methyl, R ¹⁰⁷ is an organic group having 1 to 10 carbon atoms, and m is an integer of 1 to 10.

Specific examples of the monohydroxy compound are preferably those used in the examples, and examples thereof include benzyl alcohol as an aromatic monohydric alcohol.

In addition, as specific examples of the monohydroxy compound, in addition to the compound, isopropyl alcohol as an aliphatic monohydric alcohol; benzyl alcohol and propylene glycol monoethyl ether as the compound represented by the formula (H-3) may be mentioned. , Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol ) And 3-ethyl-3-hydroxymethyloxetane; and dimethyl benzyl carbinol as an aromatic monohydric alcohol.

Among the specific examples of these monohydroxy compounds, benzyl alcohol and propylene glycol are more preferred as the compound that provides polyester amido acid (A) that has good compatibility with the epoxy group-containing copolymer (B) and is easily available. Monoethyl ether and 3-ethyl-3-hydroxymethyloxetane are particularly preferably benzyl alcohol.

When a monohydroxy compound is used as a raw material of polyester amido acid (A), the compound (a1), diamine (a2), and polyhydroxy compound (a3) having two or more acid anhydride groups are used. The total amount is 100 parts by weight, and the used amount of the monohydroxy compound is preferably 100 parts by weight or less, and more preferably 50 parts by weight or less.

<1-1-5. Monoamines having an alkoxysilyl group> In the synthesis of polyester amidinic acid (A), it is possible to include other than the above, as long as the purpose of the present invention is not impaired. Examples of other raw materials include monoamines having an alkoxysilyl group as examples of other raw materials.

Specific examples of the monoamine having an alkoxysilyl group used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-amino group. Propylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-amine Butylmethyl diethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyl Diethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. At least one of these can be used.

Among the specific examples of these monoamines having an alkoxysilyl group, compounds which are easily available and provide polyester amido acid (A) having good compatibility with the epoxy group-containing copolymer (B) are more Preferred are 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, and particularly preferred is 3-aminopropyltriethoxysilane.

When a monoamine having an alkoxysilyl group is used as a raw material of the polyester amido acid (A), the compound (a1), the diamine (a2), and the polyvalent compound have two or more acid anhydride groups. The total amount of the hydroxy compound (a3) is 100 parts by weight, and the amount of the monoamine having an alkoxysilyl group is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less.

<1-1-6. Solvents used in the synthesis reaction of polyester amidate (A)> Specific examples of the solvent used in the synthesis reaction to obtain polyester amidate (A) include the following: : Methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol Alcohol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") and cyclohexanone. Among these, MMP, diethylene glycol methyl ethyl ether, and PGMEA are preferable.

<1-1-7. Method for synthesizing polyester amidine (A)> The method for synthesizing polyester amidine (A) used in the present invention is a compound (a1) having two or more acid anhydride groups. The diamine (a2) and the polyhydroxy compound (a3) are essential components, and the reaction is performed in a solvent used in the synthesis reaction.

The preferred raw material ratio of the polyester amidate (A) is that for the X mol tetracarboxylic dianhydride, the Y mol diamine, and the Z mol polyhydric hydroxy compound, the formula (3) and the formula ( 4) The ratio of relationships established. Within this range, the solubility of the polyester amidate (A) in a solvent is high, and the coatability of the photosensitive composition on the substrate is good.

In the formula (3), 0.7 ≦ Z / Y ≦ 7.0 is preferred, and 1.0 ≦ Z / Y ≦ 5.0 is more preferred. Further, in the formula (4), 0.5 ≦ (Y + Z) /X≦4.0 is preferable, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferable.

In the synthesis of polyester amidinic acid (A), it is considered that in the range of the formula (4), under the condition that X is excessively used with respect to Y + Z, it is more than a molecule having an amine group or a hydroxyl group at the terminal. A molecule having an acid anhydride group (-CO-O-CO-) at the terminal is excessively formed. On the other hand, when reacting with such a monomer structure, if a monohydroxy compound and a monoamine having an alkoxysilyl group are added, the reaction with an acid anhydride group at the molecular terminal can be performed, and the terminal can be performed separately. Esterification and amidation. Polyesteramide (A) obtained by adding a monohydroxy compound for reaction can further improve the coatability of the photosensitive composition, and polyesterester obtained by adding a monoamine having an alkoxysilyl group for reaction Amino acid (A) can improve the adhesion between the cured film and the substrate.

If 100 parts by weight or more of the total amount of the compound (a1), the diamine (a2), and the polyhydroxy compound (a3) having two or more acid anhydride groups is used, the solvent used in the synthesis reaction is 100 parts by weight. The reaction proceeds smoothly and is therefore preferred. The reaction is preferably performed at 40 ° C to 200 ° C for 0.2 hours to 20 hours.

The order of adding raw materials to the reaction system is not particularly limited. That is, any one of the following methods can be used: a method in which a compound (a1), a diamine (a2), and a polyhydroxy compound (a3) having two or more acid anhydride groups are simultaneously added to a reaction solvent; a diamine (A2) and polyhydric hydroxyl compound (a3) A method of adding a compound (a1) having two or more acid anhydride groups after dissolving them in a reaction solvent; making a compound (a1) having two or more acid anhydride groups and a polyhydric hydroxyl compound (A3) A method of adding a diamine (a2) to a solution containing a reaction product thereof after performing a reaction in advance; or reacting a compound (a1) and a diamine (a2) having two or more acid anhydride groups in advance, A method of adding a polyhydroxy compound (a3) to a solution containing the reaction product, and the like.

In the case of reacting a monohydroxy compound, it may be added at an arbitrary time point of the reaction.

When the monoamine having an alkoxysilyl group is reacted, after the reaction of the compound (a1), the diamine (a2), and the polyhydroxy compound (a3) having two or more acid anhydride groups, the reaction will include After the solution of the reaction product is cooled to 40 ° C or lower, a monoamine having an alkoxysilyl group is added, and the reaction is preferably performed at 10 ° C to 40 ° C for 0.1 to 6 hours.

The polyester amidine (A) synthesized in the manner described above includes a structural unit represented by formula (1) and a structural unit represented by formula (2), and its terminal contains two or more An acid anhydride group, amino group, hydroxyl group, and alkoxy group of any of the acid anhydride group compound (a1), diamine (a2), polyhydroxy compound (a3), monohydroxy compound, and monoamine having an alkoxysilyl group Silyl, or additives other than these compounds.

The weight average molecular weight of the polyester amidine (A) obtained is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in these ranges, the coating property of a photosensitive composition on a base material will be favorable.

The weight average molecular weight in this specification is a value calculated in terms of polystyrene by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 mL / min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, the polystyrene calibration kit PL2010-0102 from Agilent Technologies Co., Ltd.), and the column uses PLgel MIXED-D (Agilent Technologies Co., Ltd.), Tetrahydrofuran (THF) can be used as the mobile phase for measurement. In addition, the weight average molecular weight of a commercial item in this specification is a value described in a catalog.

<1-2. Epoxy group-containing copolymer (B)> The epoxy group-containing copolymer (B) is a polymerizable compound (b2) other than the polymerizable compound (b1) and (b1) having an epoxy group. Copolymer.

At least a solvent is required for the synthesis of the epoxy group-containing copolymer (B). This solvent can be left as it is, and a liquid or gel-like epoxy group-containing copolymer solution in consideration of handling properties can be used to produce a photosensitive composition. The solvent can also be removed and used in consideration of portability, etc. Solid epoxy group-containing copolymer to produce a photosensitive composition.

<1-2-1. Polymerizable compound (b1) having epoxy group> In the present invention, as a raw material for obtaining an epoxy group-containing copolymer (B), a polymerizable compound having an epoxy group ( b1).

The polymerizable compound (b1) having an epoxy group used in the present invention is a compound having at least one epoxy group in one molecule and having at least one polymerizable group.

The polymerizable group contained in the polymerizable compound (b1) having an epoxy group used in the present invention is preferably a radical polymerizable group.

Specific examples of the polymerizable compound (b1) having an epoxy group include glycidyl methacrylate used in the examples.

In addition, as specific examples of the polymerizable compound (b1) having an epoxy group, in addition to the above-mentioned compounds, glycidyl acrylate, methyl glycidyl (meth) acrylate, and (meth) acrylic acid 3, As the 4-epoxy cyclohexyl ester, at least one of the specific examples of the polymerizable compound (b1) having an epoxy group can be used.

Among the specific examples of these polymerizable compounds (b1) having an epoxy group, the compounds are easy to obtain and provide compounds having an epoxy group-containing copolymer (B) having good compatibility with the polyester amidate (A). Is more preferably glycidyl (meth) acrylate, and particularly preferably glycidyl methacrylate.

<1-2-2. Polymerizable Compound (b2)> In the present invention, a polymerizable compound (b2) other than (b1) is used as a raw material for obtaining an epoxy group-containing copolymer (B).

The polymerizable compound (b2) used in the present invention is a compound excluding the polymerizable compound (b1) having an epoxy group among the compounds having at least one polymerizable group in one molecule.

The polymerizable group contained in the polymerizable compound (b2) used in the present invention is preferably a radical polymerizable group.

The raw material of the epoxy group-containing copolymer (B) of the present invention must contain a polymerizable compound having a phenolic hydroxyl group as the polymerizable compound (b2).

<1-2-2-1. Polymerizable compound having a phenolic hydroxyl group> The polymerizable compound having a phenolic hydroxyl group used in the present invention has at least one phenolic hydroxyl group in one molecule and has at least one polymerizable property. Compounds.

Examples of preferred compounds of the polymerizable compound having a phenolic hydroxyl group include a compound represented by the formula (5) and a compound represented by the formula (6).

Specific examples of the polymerizable compound having a phenolic hydroxyl group are preferably compounds used in the examples, and examples thereof include 4-hydroxystyrene and 4-hydroxyphenylvinyl ketone as the compound represented by the formula (5); And 4-hydroxyphenyl methacrylate as a compound represented by formula (6).

In addition, as specific examples of the polymerizable compound having a phenolic hydroxyl group, in addition to the compound, 2-hydroxystyrene, 3-hydroxystyrene, and 2-hydroxymethyl, which are compounds represented by the formula (5), can also be mentioned. Methylstyrene, 3-hydroxymethylstyrene, 4-hydroxymethylstyrene, 2-hydroxyphenylvinyl ketone, and 3-hydroxyphenylvinyl ketone; and formazan as a compound represented by formula (6) 2-hydroxyphenyl acrylate, 3-hydroxyphenyl methacrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl (meth) acrylamide, 3-hydroxyphenyl (meth) acryl Amine, 4-hydroxyphenyl (meth) acrylamide, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenylethyl (meth) acrylate, and 4-hydroxyphenyloxy (meth) acrylate As the ethyl ester, at least one of the specific examples of the polymerizable compound having a phenolic hydroxyl group can be used.

Among these specific examples of the polymerizable compound having a phenolic hydroxyl group, it is more preferable as a compound that provides an epoxy group-containing copolymer (B) that is easy to obtain and has good compatibility with polyester amidate (A). It is 4-hydroxystyrene, 4-hydroxymethylstyrene, 4-hydroxyphenylvinyl ketone, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide and (formaldehyde) 4-hydroxyphenyloxyethyl acrylate, particularly preferably 4-hydroxystyrene, 4-hydroxyphenylvinyl ketone, and 4-hydroxyphenyl (meth) acrylate.

<1-2-2-2. Polymerizable compound without polymerizable compound (b2) without phenolic hydroxyl group> As a specific example of polymerizable compound without polymerizable compound (b2) without phenolic hydroxyl group, preferable Examples include methacrylic acid, benzyl methacrylate, and N-cyclohexyl maleimide.

Moreover, as a specific example of the polymerizable compound which does not have a phenolic hydroxyl group among the polymerizable compound (b2), acrylic acid, 2-hydroxyethyl (meth) acrylate, (meth) can be mentioned besides the said compound. 2-hydroxypropyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 2-ethoxyethyl, 2- (n-propoxy) ethyl (meth) acrylate, 2- (isopropoxy) ethyl (meth) acrylate, 2- (n-butyl) (meth) acrylate Oxy) ethyl ester, 2- (isobutoxy) ethyl (meth) acrylate, 2- (second butoxy) ethyl (meth) acrylate, 2- (third butyl) (meth) acrylate (Oxy) ethyl ester, 2-phenoxyethyl (meth) acrylate, dicyclopentenyloxy (meth) acrylate, 2-methoxypropyl (meth) acrylate, (meth) Methoxy diethylene glycol acrylate, ethoxy diethylene glycol (meth) acrylate Ester, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, mono (meth) acryloxypropyl modified polydimethylsiloxane , 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, 3- [tris (triethylsilyloxy) silyl] propyl (meth) acrylate, ( 3- (trimethoxysilyl) propyl meth) acrylate and 3- (triethoxysilyl) propyl (meth) acrylate, styrene, methylstyrene, N-phenylcis butadiene As the imine, at least one of specific examples of the polymerizable compound (b2) which is not represented by any of the formula (5) and the formula (6) can be used.

Among specific examples of the polymerizable compound having no phenolic hydroxyl group among these polymerizable compounds (b2), it is easy to obtain and provides an epoxy group-containing copolymer having good compatibility with polyester amidate (A). The compound (B) is more preferably n-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, or methoxypoly (meth) acrylate Ethylene glycol ester, mono (meth) acryloxypropyl-modified polydimethylsiloxane, 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, Styrene, N-cyclohexyl-cis-butenediamidoimide and N-phenyl-cis-butenediamidoimine, particularly preferably n-butyl (meth) acrylate, benzyl (meth) acrylate, (methyl) ) Dicyclopentenyloxyethyl acrylate, methoxypolyethylene glycol (meth) acrylate, N-cyclohexylcis-butenedifluoreneimine and N-phenylcisbutenedifluoreneimine.

Moreover, among the specific examples of the polymerizable compound which does not have a phenolic hydroxyl group among these polymerizable compounds (b2), it is easy to obtain, and it is excellent in a developing solution when it produces an epoxy group containing copolymer (B). Soluble compounds are more preferably (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and 3- (trimethoxysilyl) (meth) acrylate The propyl ester is particularly preferably (meth) acrylic acid or 2-hydroxyethyl (meth) acrylate.

<1-2-3. Solvent used in polymerization reaction of epoxy group-containing copolymer (B)> Specific examples of the solvent used in polymerization reaction to obtain epoxy group-containing copolymer (B) Examples, preferably ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetic acid Methyl ester, ethyl ethoxylate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, MMP, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl Acetate, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-hydroxy-2-methylpropionate, 2-hydroxyl Ethyl-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxyl 4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate , Cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether ethyl Acid esters, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether.

<1-2-4. Polymerization method of epoxy group-containing copolymer (B)> The polymerization method of epoxy group-containing copolymer (B) used in the present invention is a polymerizable compound having an epoxy group. (B1) and a polymerizable compound having a phenolic hydroxyl group are necessary raw materials, and the reaction is performed in a solvent used in the polymerization reaction.

About the preferable raw material ratio of the epoxy group containing copolymer (B), the polymerizable compound (b1) and the polymerizable compound (b2) which have an epoxy group have the polymerizability of an epoxy group in 100 weight% of the total amount The compound is 20 to 90% by weight, and the polymerizable compound having a phenolic hydroxyl group is 1 to 40% by weight. Within this range, the linearity of the shape of the line pattern during short-time development of the photosensitive composition is particularly good.

The reaction proceeds smoothly if 100 parts by weight or more of the solvent used in the polymerization reaction is used with respect to 100 parts by weight of the total amount of the polymerizable compound (b1) and the polymerizable compound (b2) having an epoxy group. . The reaction is preferably performed at 40 ° C to 200 ° C for 0.2 hours to 20 hours.

The polymerization method of the epoxy group-containing copolymer (B) is not particularly limited, but is preferably a radical polymerization in a solution using a solvent. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated by the polymerization initiator used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours. Moreover, the polymerization can be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

<1-3.1,2-quinonediazide compound (C)> The 1,2-quinonediazide compound (C) used in the present invention has at least one 1,2-quinonediazide in one molecule. Compounds.

The 1,2-quinonediazide compound (C) is suitable for use because a condensate of a compound having a phenolic hydroxyl group and a sulfonyl chloride having a 1,2-quinonediazide group is easily available.

Specific examples of the compound having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'- Tetrahydroxybenzophenone, 2,3,3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) Methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane , 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4 , 4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol, bis (2,5-dimethyl-4- (Hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'- Hexanol (3,3,3 ', 3'-tetramethyl-1,1'-spirobiinden-5,6,7,5', 6 ', 7'-hexanol), 2,2,4-trimethyl- 7,2 ', 4'-trihydroxyflavan (2,2,4-trimethyl-7,2', 4'-trihydroxyflavan).

Specific examples of the sulfonyl chloride having a 1,2-quinonediazide group include 1,2-naphthoquinonediazide-4-sulfonyl chloride and 1,2-naphthoquinonediazide-5-sulfonate.醯 Chlorine.

Specific examples of the 1,2-quinonediazide compound (C) used as a specific example of these compounds having a phenolic hydroxyl group and a specific example of a sulfonyl chloride having a 1,2-quinonediazide group are preferably List 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol and 1,2- used in the examples Condensate of naphthoquinonediazide-5-sulfonyl chloride.

As a specific example of using these compounds having a phenolic hydroxyl group and a specific example of a sulfonyl chloride having a 1,2-quinonediazide group, the 1,2-quinonediazide compound (C) is easily obtained and is compatible with the polymerization. A compound having good compatibility with ester amidate (A), more preferably 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl ] Ethylene] bisphenol and 1,2-naphthoquinonediazide-4-sulfonyl chloride condensate and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1 -Methylethyl] phenyl] ethylene] bisphenol and 1,2-naphthoquinonediazide-5-sulfosulfonyl chloride, particularly preferably 4,4 '-[1- [4- [ Condensate of 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonyl chloride.

<1-4. Additives> Various additives can be added to the photosensitive composition of the present invention in order to improve coating uniformity, adhesion, heat resistance, hardenability, and resistance to ultraviolet deterioration. Examples of additives include coupling agents such as anionic, cationic, nonionic, fluorine or silicon based leveling agents / surfactants, silane coupling agents, hindered phenols, hindered amines, phosphorus, sulfur Based compounds such as antioxidants, epoxy hardeners, UV absorbers, anticoagulants, thermal crosslinkers, and epoxy compounds other than epoxy-containing copolymers (B).

<1-4-1. Surfactant> In order to improve coating uniformity, a surfactant may be added to the photosensitive composition of the present invention. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, and Polyflow ) No. 90, Polyflow No. 95 (both trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Disperbyk 181, Disperbyk 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK- 361N, BYK-UV3500, BYK-UV3570 (all are trade names; BYK Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50 -100CS (both trade names; Shin-Etsu Chemical Industry Co., Ltd.), Surflon-SC-101, Surflon-KH-40, Surflon-S611 (all Trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM , Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (both trade names; Neos Corporation), Ai EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (all Are trade names; Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430 , Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac ) F-553, Megafac F-554, Megafac F -555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-30, Megafac R-94, Megafac (Megafac) RS-75, Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names; DIC) stock limited Company), 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; Evonik-Degussa Japan ) Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, two Glycerin tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene Alkenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauric acid Ester, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oil Acid esters, sorbitan fatty acid esters, polyoxyethylene 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.

Specific examples of these surfactants are selected from BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surflon-S611, and Ftergent. ) 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Mega (Megafac) F-559, Megafac RS-72-k, Megafac DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylic acid At least one of a salt, a fluoroalkyl polyoxyethylene ether, a fluoroalkyl sulfonate, a fluoroalkyl trimethylammonium salt, and a fluoroalkylamino sulfonate will increase the uniformity of coating of the photosensitive composition , So it is preferred.

The content of the surfactant in the photosensitive composition of the present invention is preferably 0.01 to 10% by weight based on the total amount of the photosensitive composition.

<1-4-2. Coupling agent> From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the photosensitive composition of the present invention may further contain a coupling agent.

As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy Silane (eg, trade name; Sila-Ace S510, JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (eg, trade name ; Sila-Ace S530, JNC Co., Ltd., 3-mercaptopropyltrimethoxysilane (for example, trade name; Sila-Ace S810, Jenzhi ( (JNC) Co., Ltd.), copolymers of 3-glycidyloxypropyltrimethoxysilane (for example, trade name; CoatOSil MP200, Momentive Performance Materials Co., Ltd.) and other silanes Coupling agents, aluminum coupling agents such as aluminum alkoxydiisopropoxide, and titanate coupling agents such as tetraisopropylbis (dioctylphosphite) titanate.

Among these, 3-glycidoxypropyltrimethoxysilane 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 based on the total amount of the photosensitive composition, which is preferable because the adhesion between the formed cured film and the substrate is improved.

<1-4-3. Antioxidant> From the viewpoint of improving heat resistance, the photosensitive composition of the present invention may further contain an antioxidant.

To the photosensitive composition of the present invention, antioxidants such as hindered phenol-based, hindered amine-based, phosphorus-based, and sulfur-based compounds may be added. Among these, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, and Yilu Jia Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Yilujia Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Yilu Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yilu Irganox 565DD, Irganox 295 (both trade names; BASF Japan), ADK STAB AO-20, Adikos ADK STAB AO-30, ADK STAB AO-50, ADK STAB ) AO-60, ADK STAB AO-70, ADK STAB AO-80 (both trade names; ADEKA Co., Ltd.). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

An antioxidant is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

<1-4-4. Epoxy hardener> In order to improve hardenability, the photosensitive composition of the present invention may further contain an epoxy hardener. As the epoxy hardener, there are thermosensitive properties such as an acid anhydride hardener, an amine hardener, a phenol hardener, an imidazole hardener, a catalyst hardener, and a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a sulfonium salt. The acid generator and the like are preferably an acid anhydride-based hardener or an imidazole-based hardener from the viewpoint of compatibility with the polyester amido acid (A).

Specific examples of the acid anhydride-based hardener include aliphatic dicarboxylic acid anhydrides (for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic acid). Acid anhydride, hexahydrotrimellitic anhydride, etc.), aromatic polycarboxylic anhydride (eg, phthalic anhydride, trimellitic anhydride, etc.). Among these, trimellitic anhydride and hexahydrotrimellitic anhydride which can improve the hardenability without impairing the solubility of the photosensitive composition in a solvent are preferred.

Specific examples of the imidazole-based hardener include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-diimidazole. Hydrogen-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these, 2-undecylimidazole which can improve the curability without impairing the solubility of the photosensitive composition in a solvent is preferable.

The ratio of the epoxy curing agent to the epoxy group-containing copolymer (B) is 100 parts by weight relative to the epoxy group-containing copolymer (B), and the epoxy curing agent is 0.1 to 60 parts by weight.

<1-4-5. Ultraviolet absorber> The photosensitive composition of the present invention may further include an ultraviolet absorber from the viewpoint of further improving the ultraviolet deterioration resistance of the formed cured film.

Specific examples of the ultraviolet absorber include: TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234 , TINUVIN 326, TINUVIN 571, TINUVIN 765 (both trade names; BASF Japan Co., Ltd.).

0.01 to 10 parts by weight of an ultraviolet absorber is added to the total amount of the photosensitive composition and used.

<1-4-6. Anti-agglomerating agent> The photosensitive composition of the present invention may further include an anti-agglomerating agent from the standpoint of not fusing solid components with a solvent and preventing aggregation.

Specific examples of the anti-coagulant include Disperbyk-145, Disperbyk-161, Disperbyk-162, and Disperbyk-162. Disperbyk-163, Disperbyk-164, Disperbyk-182, Disperbyk-184, Disperbyk-185, Dis Disperbyk-2163, Disperbyk-2164, BYK-220S, Disperbyk-191, Disperbyk-199, Dispar Disperbyk-2015 (all are trade names; BYK Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names; Neos Co., Ltd.), Flowlen G-600, Flowlen G-700 (all are trade names; Gongrongshe Chemical Co., Ltd.).

0.01 to 10 parts by weight of an anti-agglomerating agent is added to the total amount of the photosensitive composition and used.

<1-4-7. Thermal crosslinking agent> From the viewpoint of further improving the hardenability and heat resistance, the photosensitive composition of the present invention may further include a thermal crosslinking agent.

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

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

<1-4-8. Epoxy compounds other than epoxy-group-containing copolymer (B)> In order to improve hardenability, the photosensitive composition of the present invention may further contain epoxy-group-containing copolymer (B) Epoxy compound.

0.1 to 50 parts by weight of a ring other than the epoxy group-containing copolymer (B) is added to 100 parts by weight of the total amount of the polyester amidate (A) and the epoxy group-containing copolymer (B). Oxygen compounds.

Examples of epoxy compounds other than the epoxy group-containing copolymer (B) include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, and biphenyl type rings. Oxygen compounds, phenol novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, and alicyclic epoxy compounds.

Specific examples of commercially available bisphenol A-type epoxy compounds include jER 828, jER 1004, and jER 1009 (both trade names; Mitsubishi Chemical Corporation); as commercially available bisphenol F-type epoxy compounds, Specific examples include jER 806 and jER 4005P (both are trade names; Mitsubishi Chemical Corporation); and as specific examples of commercially available glycidyl ether epoxy compounds, Tecmoa VG3101L (product Name; Printec Co., Ltd.), EPPN-501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), jER 1032H60 (trade name; Mitsubishi Chemical Co., Ltd.); as the city Specific examples of commercially available biphenyl epoxy compounds include jER YX4000, jER YX4000H, and jER YL6121H (both are trade names; Mitsubishi Chemical Corporation); as specific examples of commercially available phenol novolac epoxy compounds, Examples include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152, jER 154 (both trade names; Mitsubishi Chemical Corporation); as commercially available cresol novolac type Specific examples of the oxygen compound include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (all are trade names; Nippon Kayaku Co., Ltd.); and commercially available bisphenol A novolac epoxy compounds Specific examples include jER 157S65, jER 157S70 (both are trade names; Mitsubishi Chemical Corporation); and specific examples of commercially available alicyclic epoxy compounds include Celloxide 2021P, Rosiede (Celloxide) EHPE-3150 (both trade names; Daicel Corporation). In addition, Tecmoa VG3101L, which is a glycidyl ether type epoxy compound, is 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-cyclo Oxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] A mixture of phenoxy] -2-propanol.

<1-5. Solvents arbitrarily added to the photosensitive composition> In the photosensitive composition of the present invention, the solvent used for the synthesis reaction of the polyester amidate (A) is removed and the epoxy group-containing copolymerization is used. In addition to the solvent used in the polymerization reaction of the substance (B), a solvent may be added. The solvent arbitrarily added to the photosensitive composition of the present invention (hereinafter referred to as "solvent for dilution") is preferably a soluble polyester amido acid (A), an epoxy group-containing copolymer (B), and 1,2 -Solvents such as quinonediazide (C). Specific examples of the solvent for dilution include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, and methoxyacetic acid. Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, MMP, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate , Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropane Methyl ester, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methylpyruvate Esters, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl 2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether Ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether can be used as the solvent for dilution At least one of the specific examples.

<1-6. Preservation of Photosensitive Composition> When the photosensitive composition of the present invention is stored in a range of -30 ° C to 25 ° C, the stability of the composition over time is improved, which is preferable. When the storage temperature is -20 ° C to 10 ° C, no precipitates are present and it is more preferable.

<2. Cured film of photosensitive composition> The photosensitive composition of the present invention can be obtained by polyester polyester amine acid (A), epoxy group-containing copolymer (B), and 1,2- The quinonediazide compound (C) and additives are mixed, and a solvent for dilution is optionally added as needed, and these are mixed and dissolved uniformly. As an additive, a coupling agent, a surfactant, and other additives may be selected and used according to the desired characteristics.

The photosensitive composition prepared in the manner described above (in the case of a solid state without a solvent, after being dissolved in a solvent) is applied to the surface of a substrate, and the solvent is removed by, for example, heating. membrane. The conventionally known methods such as a spin coating method, a roll coating method, a dipping method, a flexographic printing method, a spray method, and a slit coating method can be used for coating the photosensitive composition on the substrate surface. Next, the coating film is heated (pre-baked) using a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio. Usually, it is 70 ° C to 150 ° C. If it is an oven, it is 5 minutes to 15 minutes. If it is a hot plate, it is 1 minute to 5 minutes.

Thereafter, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet irradiation is preferably 5 mJ / cm ² to 1,000 mJ / cm ² in an i-ray meter. The photosensitive composition in the portion irradiated with the ultraviolet rays is soluble in the alkaline developing solution because the alkali solubility of the 1,2-quinonediazide compound is improved.

Next, the coating film is immersed in an alkaline developing solution by spray development, spray development, coating development, dip development, or the like, and unnecessary portions are dissolved and removed. Specific examples of the alkaline developer are aqueous solutions of inorganic bases such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic bases such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, a surfactant, and the like may be added to the alkaline developing solution and used.

Finally, in order to completely harden the coating film, a hardened film may be obtained by heat treatment at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and in an oven, for 30 minutes to 90 minutes, If it is a hot plate, it is performed for 5 to 30 minutes.

When the cured film obtained as described above is heated, further 1) the polyamidic acid of the polyester phosphoamic acid (A) is partially dehydrated and cyclized to form a phosphonium imine bond, and 2) the polyester phosphoamino acid (A) The carboxyl group reacts with the epoxy group-containing copolymer (B) and has a high molecular weight, so it is very tough and excellent in heat resistance. Therefore, the cured film of the present invention is effective if it is used as a protective film for a color filter, and a color filter can be used to produce a liquid crystal display element or a solid-state imaging element. Except for a protective film for a color filter, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode, or formed between a transparent electrode and an alignment film Insulation film is effective. Furthermore, the cured film of this invention is effective even if it is used as a protective film of LED light emitting body. [Example]

Next, the present invention will be specifically described with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples. However, the present invention is not limited to these examples.

The compounds used in the reference synthesis examples, synthesis examples, comparative synthesis examples, reference examples, examples, and comparative examples are described in advance for each component.

Tetracarboxylic dianhydride in the compound (a1) having two or more acid anhydride groups: a1-1: ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride a1-2: BT -100: styrene-maleic anhydride copolymer in compound (a1) having 1,2,3,4-butanetetracarboxylic dianhydride having two or more acid anhydride groups: a1-3: trade name SMA -1000P, Sartomer Co., Ltd., abbreviated as "SMA-1000P" Diamine (a2): a2-1: DDS: 3,3'-diaminodiphenylphosphonium polyhydroxy compound (a3 ): A3-1: 1,4-butanediol monohydroxy compound: a4-1: benzyl alcohol polyester amidate (A) used in the synthesis reaction of the solvent: MMP: 3-methoxypropanoic acid methyl Ester PGMEA: propylene glycol monomethyl ether acetate

Polymerizable compound (b1) having epoxy group: b1-1: glycidyl methacrylate and other polymerizable compound (b2): polymerizable compound having phenolic hydroxyl group: b2-1: 4-hydroxystyrene b2 -2: 4-hydroxyvinyl ketone b2-3: 4-hydroxyphenyl methacrylate other polymerizable compounds (b2) Polymerizable compounds without phenolic hydroxyl groups: b2-4: methacrylic acid b2-5 : Benzyl methacrylate b2-6: N-cyclohexylcis-butenediamidine imide-containing copolymer (B) Polymerization initiator used in the polymerization reaction: 2,2'-azo Bis (2-methylpropionic acid) dimethyl ester (trade name V-601, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as "V-601") Polymerization reaction of epoxy-containing copolymer (B) Solvents used: PGMEA: propylene glycol monomethyl ether acetate

1,2-quinonediazide compound (C): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bis Condensate of phenol and 1,2-naphthoquinonediazide-5-sulfonyl chloride (average esterification rate 58%, hereafter referred to as "PAD")

Dilution solvent: PGMEA: propylene glycol monomethyl ether acetate

Additive-1: 3-glycidyloxypropyltrimethoxysilane (trade name; Sila-Ace) S510 as a silane-based coupling agent, JNC Corporation, abbreviated as "S510") Additive-2: Megafac F-556 (trade name, DIC Corporation, hereinafter referred to as "F-556") as a fluorine-based surfactant

As shown below, polyester lysine solutions containing reaction products such as tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound were synthesized (Synthesis Example 1 and Synthesis Example 2).

[Synthesis Example 1] Synthesis of polyester lysine solution (A1) In a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input addition port, and a nitrogen introduction port, 446.96 g was added as a solvent used in the synthesis reaction. MMP, 31.93 g of 1,4-butanediol as a polyhydroxy compound, 25.54 g of benzyl alcohol as a monohydroxy compound, and 183.20 g of ODPA as a tetracarboxylic dianhydride under a stream of dry nitrogen at 130 ° C Stir for 3 hours. Thereafter, the solution after the reaction was cooled to 25 ° C., 29.33 g of DDS as diamine and 183.04 g of MMP were charged, stirred at 20 ° C. to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour, and cooled to At 30 ° C. or lower, a 30% by weight solution (A1) of a pale yellow transparent polyester amidine was obtained. The weight average molecular weight measured by GPC was 4,200. [Z / Y = 3, (Y + Z) /X=0.8]

In addition, the "30% by weight solution of polyester amido acid (A1)" herein means that the weight of the solid component and the weight of the solvent are calculated by considering that all the compounds added as described above are reacted. The obtained concentration was 30% by weight. The same applies to the following synthesis examples and comparative synthesis examples.

[Synthesis Example 2] Synthesis of polyester lysine solution (A2) In a 1,000 mL four-necked flask equipped with a thermometer, a stirrer, a raw material input addition port, and a nitrogen introduction port, 604.80 g was added as a solvent used in the synthesis reaction. PGMEA, 34.47 g of BT-100 as tetracarboxylic dianhydride, 164.11 g of SMA-1000P as styrene-maleic anhydride copolymer, 50.17 g of benzyl alcohol as monohydroxy compound, 10.45 g of 1,4-butanediol, which is a polyhydroxy compound, was stirred at 130 ° C. for 3 hours under a stream of dry nitrogen. Thereafter, the solution after the reaction was cooled to 25 ° C., 10.80 g of DDS as diamine and 25.20 g of PGMEA were charged, stirred at 20 ° C. to 30 ° C. for 2 hours, and then stirred at 115 ° C. for 1 hour, and cooled to At 30 ° C or lower, a 30% by weight solution (A2) of a pale yellow transparent polyester amidine was thus obtained. The weight average molecular weight measured by GPC was 10,000. [Z / Y = 2.7, (Y + Z) /X=0.9]

An epoxy group-containing copolymer solution (Synthesis Example 3 to Synthesis Example 12 and Comparative Synthesis Example) containing a reaction product of a polymerizable compound (b1) and a polymerizable compound (b2) having an epoxy group was synthesized as shown below. 1 to Comparative Synthesis Example 2).

[Synthesis Example 3] Synthesis of epoxy group-containing copolymer solution (B1) In a four-necked flask equipped with a stirrer, PGMEA was added as a solvent used in the polymerization reaction with the following composition, and as an epoxy group-containing Glycidyl methacrylate of the polymerizable compound (b1), 4-hydroxystyrene which is a polymerizable compound having a phenolic hydroxyl group among the other polymerizable compounds (b2), and The polymerizable compound having a phenolic hydroxyl group, methacrylic acid and benzyl methacrylate, and V-601 as a polymerization initiator were heated at 80 ° C for 3 hours, and then heated at 90 ° C for 1 hour. Glycidyl methacrylate 70.80 g 4-hydroxystyrene 4.80 g Methacrylic acid 8.40 g Benzyl methacrylate 36.00 g V-601 18.00 g PGMEA 280.00 g The solution after the polymerization reaction is cooled to room temperature to obtain a ring-containing A 30% by weight solution (B1) of an oxy-copolymer. The weight average molecular weight determined by GPC analysis was 17,000.

[Synthesis Example 4 to Synthesis Example 10, Reference Synthesis Example 1 to Reference Synthesis Example 3, and Comparative Synthesis Example 1 to Comparative Synthesis Example 2] According to the method of Synthesis Example 3, each of the ratios (unit: g) described in Table 1 was used. A component was set as a raw material, and the polymerization reaction was performed, and the epoxy group containing copolymer solution was obtained. Moreover, the weight average molecular weight of the obtained epoxy group containing copolymer is also shown in Table 1.

[表 1] Table 1

[Reference Example 1] A polyester amidate solution (A1) as a polyester amidate (A) and an epoxy group-containing copolymer solution as an epoxy group-containing copolymer (B) were mixed and dissolved in the following composition. (B'1), PAD as a 1,2-quinonediazide compound (C), S510 and F-556 as additives, and PGMEA as a solvent for dilution, thereby obtaining a photosensitive composition. Polyester amine solution (A1) 20.00 g Epoxy group-containing copolymer solution (B'1) 30.00 g PAD 2.40 g S510 0.30 g F-556 0.03 g PGMEA 10.51 g

In addition, the total amount of the solvents contained in the composition is MMP contained in the polyester glutamic acid solution (A1), PGMEA contained in the epoxy-group-containing copolymer solution (B'1), and dilution The total amount of the solvent PGMEA was adjusted to a solid content concentration of about 28% by weight in this step. The same applies to Reference Example 2 and below, and in Examples and Comparative Examples.

The photosensitive composition was spin-coated on a glass substrate at 700 rpm for 10 seconds, and pre-baked on a hot plate at 100 ° C for 2 minutes. Next, in the air, a mask with a line pattern with a width of 50 μm was used, and a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) was used to pass 350 nm through a wavelength cutoff filter. The following light is cut off, and g-rays, h-rays, and i-rays are taken out and exposed. The exposure amount was measured using a cumulative light meter UIT-102 (trade name; Ushio (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio (USHIO) Co., Ltd.) to determine the exposure amount to 200 mJ / cm ² . The exposed coating film was developed with a 2.38% by weight tetramethylammonium hydroxide aqueous solution for 60 seconds, and then the coating film was washed with pure water for 20 seconds, and then dried with a 100 ° C. hot plate for 2 minutes. After further baking in an oven at 230 ° C. for 30 minutes, a glass substrate with a cured film having a film thickness of 3.0 μm and a line pattern having a pattern width of approximately 50 μm was obtained.

[Evaluation method of heat resistance] After the obtained glass substrate with a cured film having a line pattern was reheated at 240 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured, and calculated as follows Formula to calculate the residual film rate. For the measurement of the film thickness, a step / surface roughness / fine shape measuring device (trade name; P-16 +, KLA TENCOR Co., Ltd.) was used. A case where the residual film rate after heating was 95% or more was evaluated as ○, and a case where the residual film rate after heating was less than 95% was evaluated as x. Residual film rate = (film thickness after heating / film thickness before heating) × 100%

[Confirmation method of presence or absence of moire in line pattern shape] The pattern of the obtained glass substrate with a cured film having a line pattern was observed using an optical microscope, and the presence or absence of moire in the line pattern shape was confirmed. FIG. 1 is a state where there is no ripple in the shape of the line pattern, and FIG. 2 is a state where there is ripple in the shape of the line pattern.

[Reference Example 2 to Reference Example 3] According to the method of Reference Example 1, each component was mixed and dissolved at a ratio (unit: g) shown in Table 2 to obtain a photosensitive composition.

Table 2 shows the evaluation results of the heat resistance using the photosensitive composition in Reference Example 2 to Reference Example 3 and the results of confirming the presence or absence of moire in the line pattern shape.

[表 2] Table 2

[Example 1 to Example 8 and Comparative Example 1 to Comparative Example 2] According to the method of Reference Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 2 to obtain a photosensitive composition.

Using the obtained photosensitive composition, according to the method of Reference Example 1, a glass substrate with a cured film having a line pattern having a pattern width of approximately 50 μm was obtained. Among them, in the method of Reference Example 1, the time of the development step of performing the liquid-covering development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds was changed from 60 seconds to 30 seconds.

Using these obtained glass substrates with a cured film having a line pattern, the heat resistance was evaluated according to the method of Reference Example 1 and the presence or absence of ripples in the shape of the line pattern was confirmed. These results are described in Table 2.

[Method for evaluating linearity of line pattern shape during short-time development] In Examples 1 to 8 and Comparative Examples 1 to 2 in which the time of the developing step was 30 seconds, when there was no ripple in the shape of the line pattern, The linearity of the linear pattern shape during the short-time development was evaluated as ○, and when there was a ripple in the linear pattern shape, the linearity of the linear pattern shape during the short-time development was evaluated as ×.

Reference Example 1 regarding a photosensitive composition containing no polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy group-containing copolymer (B) under the condition that the development step time is 60 seconds, and No difference was observed between Reference Examples 2 to 3 of the photosensitive composition containing a polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy-based copolymer (B).

Under the condition that the development time was shortened to 30 seconds, in Comparative Example 1 regarding a photosensitive composition containing no polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy group-containing copolymer (B), a line was observed Problems with moire in the pattern shape. However, in Examples 1 to 8 regarding the photosensitive composition containing the polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy group-containing copolymer (B), no waviness occurred in the line pattern shape. problem.

Based on the results under the condition that the development time is 60 seconds and the results that the development time is 30 seconds, when the time of the manufacturing step is required to be shortened, the linearity of the line pattern shape at the time of short-time development, Clear superiority was observed in Examples 1 to 8.

In addition, it was found that the heat resistance of Comparative Example 2 regarding the photosensitive composition containing no polyester amidate (A) was poor. [Industrial availability]

The cured film obtained from the photosensitive composition of the present invention has high heat resistance and excellent linearity in the shape of the line pattern during short-term development. From this viewpoint, it can be used as a color filter, an LED light-emitting element, and a light-receiving element. Protective films of various optical materials, and insulating films formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

no

FIG. 1 is an optical microscope photograph obtained by photographing a state without moiré in the pattern shape on the line. FIG. 2 is an optical microscope photograph obtained by photographing a state of moire in a line pattern shape.

Claims (7)

A photosensitive composition comprising a polyester amido acid (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C), and the characteristics of the photosensitive composition The polyester amidate (A) includes a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): the epoxy-group-containing copolymer (B) is A copolymer of a polymerizable compound (b1) other than the polymerizable compound (b1) and (b1) having an epoxy group; and the polymerizable compound (b2) includes a polymerizable compound having a phenolic hydroxyl group, In formula (1), R ¹ is an organic group having 2 to 1000 carbons, and R ² is an organic group having 2 to 100 carbons; In formula (2), R ³ is an organic group having 2 to 1000 carbons, and R ⁴ is an organic group having 2 to 100 carbons. The photosensitive composition according to item 1 of the scope of patent application, wherein the structural unit represented by the formula (1) is a compound (a1) and a diamine (a2) having two or more acid anhydride groups as raw materials. The structural unit represented by the formula (2) is a structural unit in which a compound (a1) and a polyhydroxy compound (a3) having two or more acid anhydride groups are used as raw materials. The photosensitive composition according to item 2 of the scope of patent application, wherein the compound (a1) having two or more acid anhydride groups is selected from a tetracarboxylic dianhydride and a styrene-maleic anhydride copolymer. One or more compounds of the above; the polyester amidate (A) is a tetracarboxylic dianhydride containing X mole and Y mole in a ratio that satisfies the relationship of the following formula (3) and formula (4): The reaction product of the raw materials of the diamine of the ear and the polyhydric hydroxy compound of Z mole is 0.2 ≦ Z / Y ≦ 8.0 (3) 0.2 ≦ (Y + Z) /X≦5.0 • (4). The photosensitive composition according to claim 1, wherein the polymerizable compound (b1) having an epoxy group is one or more selected from (meth) acrylates having an epoxy group; The polymerizable compound of a hydroxyl group is one or more selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (6), In formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbons, R ⁶ is a single bond or -C (= O)-, and R ⁷ to R ¹¹ are each independently a hydroxyl group or a carbon number 1 to An organic group of 7, wherein at least one of R ⁷ to R ¹¹ is a hydroxyl group; In formula (6), R ¹² is hydrogen or an organic group having 1 to 7 carbon atoms, R ¹³ is -O- or -NH-, and R ¹⁴ is a single bond or a divalent organic group having 1 to 40 carbon atoms, R ¹⁵ to R ¹⁹ are each independently a hydroxyl group or an organic group having 1 to 7 carbon atoms, and at least one of R ¹⁵ to R ¹⁹ is a hydroxyl group. The photosensitive composition according to item 4 of the scope of application for a patent, wherein the (meth) acrylate having an epoxy group is glycidyl (meth) acrylate; the compound represented by the formula (5) is One or more members selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenylvinyl ketone; The compound represented by the formula (6) is selected from 4-hydroxy (meth) acrylic acid One or more of phenyl ester, 4-hydroxyphenyl (meth) acrylamide, and 4-hydroxyphenyloxyethyl (meth) acrylate. The photosensitive composition according to item 1 of the scope of the patent application, wherein the epoxy group-containing copolymer is 100% by weight of the total amount of the polyester amidate (A) and the epoxy group-containing copolymer (B). The content of (B) is 20% to 90% by weight, and 1,2-quinone di is 100 parts by weight based on 100 parts by weight of the total of the polyester amidate (A) and the epoxy group-containing copolymer (B). The azide compound (C) is 5 to 40 parts by weight. A cured film obtained from the photosensitive composition according to any one of claims 1 to 6 of the scope of patent application.