JP2018010066A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for a protective film that has excellent heat resistance and has excellent linearity of a line pattern shape in short-time development.SOLUTION: A photosensitive composition contains polyester amide acid (A) containing constitutional units represented by formula (1) and formula (2), an epoxy group-containing copolymer (B) that is a copolymer of a polymerizable compound having an epoxy group and a polymerizable compound having a phenolic hydroxyl group, and 1, 2-quinonediazide compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive composition used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a display element, or a protective film for a color filter. The present invention relates to an object, a cured film thereby, and an electronic component having the cured film.

A photosensitive composition is used when a protective film is formed only in a necessary portion or when a hole pattern is formed in an insulating film. An example of the photosensitive composition is an acrylic positive photosensitive composition (Patent Document 1). As the required characteristics of reliability required for displays improve, the heat resistance required for display members has improved, and the material described in Patent Document 1 has a problem of further increasing heat resistance. In order to solve the problem, a polyesteramide acid-based positive photosensitive composition having good heat resistance has been proposed (Patent Document 2). In order to cope with the recent price reduction of displays, the time of each process has been shortened in order to increase the number of manufactured units per unit time. Among them, the positive photosensitive composition described in Patent Document 2 has a problem that the line pattern shape does not become a straight line but becomes a wavy shape when the development time is short. If the line pattern shape is wavy, the panel display quality is degraded.

JP-A-5-165214 JP2008-102351

An object of the present invention is to provide a photosensitive composition for a protective film or an insulating film having good heat resistance and good line pattern shape linearity during short-time development.

As a result of intensive studies to solve the above problems, the present inventors have obtained a composition containing a polyester amide acid, an epoxy group-containing copolymer, and a 1,2-quinonediazide compound, and curing the composition. It has been found that the above object can be achieved by the cured film, and the present invention has been completed.
The present invention includes the following configurations.

式（１）において、Ｒ^１は炭素数２〜１０００の有機基であり、Ｒ^２は炭素数２〜１０００の有機基であり；

式（２）において、Ｒ^３は炭素数２〜１０００の有機基であり、Ｒ^４は炭素数２〜１００の有機基である。 [1] A photosensitive composition comprising a polyester amide acid (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C);
The polyester amide 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 a copolymer of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) other than (b1);
The polymerizable compound (b2) is a photosensitive composition containing a polymerizable compound having a phenolic hydroxyl group.

In Formula (1), R ¹ is an organic group having ² to 1000 carbon atoms, and R ² is an organic group having ² to 1000 carbon atoms;

In Formula (2), R ³ is an organic group having 2 to 1000 carbon atoms, and R ⁴ is an organic group having 2 to 100 carbon atoms.

[2] The structural unit represented by the formula (1) is a structural unit using a compound (a1) having two or more acid anhydride groups and a diamine (a2) as raw materials;
The structural unit represented by the formula (2) is a structural unit using a compound (a1) having two or more acid anhydride groups and a polyvalent hydroxy compound (a3) as raw materials. Photosensitive composition.

[3] The compound (a1) having two or more acid anhydride groups is one or more compounds selected from a tetracarboxylic dianhydride and a styrene-maleic anhydride copolymer;
The polyester amic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric hydroxy compound, and the following formulas (3) and (4) are satisfied. The photosensitive composition as described in the item [2], which is a reaction product of a raw material contained in such a ratio.

0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦5.0 (4)

式（５）において、Ｒ^５は水素又は炭素数１〜７の有機基であり、Ｒ^６は単結合又は−Ｃ（＝Ｏ）−であり、Ｒ^７〜Ｒ^１１はそれぞれ独立に、水酸基又は炭素数１〜７の有機基である。但し、Ｒ^７〜Ｒ^１１の内、少なくとも１つは水酸基であり；

式（６）において、Ｒ^１２は水素又は炭素数１〜７の有機基であり、Ｒ^１３は−Ｏ−又は−ＮＨ−であり、Ｒ^１４は単結合又は炭素数１〜４０の２価の有機基であり、Ｒ^１５〜Ｒ^１９はそれぞれ独立に、水酸基又は炭素数１〜７の有機基である。但し、Ｒ^１５〜Ｒ^１９の内、少なくとも１つは水酸基である。 [4] The polymerizable compound (b1) having an epoxy group is one or more selected from (meth) acrylates having an epoxy group;
The photosensitive property according to item [1], wherein the polymerizable compound having a phenolic hydroxyl group is one or more selected from a compound represented by the following formula (5) and a compound represented by the following formula (6). Composition.

In Formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbon atoms, R ⁶ is a single bond or —C (═O) —, and R ^{7 to} R ¹¹ are each independently a hydroxyl group or It is a C1-C7 organic group. Provided that 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 divalent having 1 to 40 carbon atoms. It is an organic group, and R ^{15 to} R ¹⁹ are each independently a hydroxyl group or an organic group having 1 to 7 carbon atoms. However, at least one of R ^{15 to} R ¹⁹ is a hydroxyl group.

[5] The (meth) acrylate having an epoxy group is glycidyl (meth) acrylate;
The compound represented by the formula (5) is one or more selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenyl vinyl ketone;
The compound represented by the formula (6) is one or more selected from 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide, and 4-hydroxyphenyloxyethyl (meth) acrylate, The photosensitive composition as described in item [4].

[6] The content of the epoxy group-containing copolymer (B) is 20 to 90% by weight in the total amount of 100% by weight of the polyester amic acid (A) and the epoxy group-containing copolymer (B). The photosensitive composition as described in the item [1], wherein the 1,2-quinonediazide compound (C) is 5 to 40 parts by weight relative to 100 parts by weight of the total amount of (A) and the epoxy group-containing copolymer (B). .

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

The photosensitive composition according to a preferred embodiment of the present invention is a material having good heat resistance and good line pattern shape linearity during short-time development, and when used as a color filter protective film of a color display element. Thus, reliability and display quality can be improved, and productivity at the time of manufacturing the color filter protective film can be improved. It can also be used as a protective film and insulating film for various optical materials.

It is the optical microscope photograph which image | photographed the state without a wave pattern in a line pattern shape.

It is the optical microscope photograph which image | photographed the state with a wave pattern in a line pattern shape.

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, “(meth) acrylate” may be used to indicate one or both of “acrylate” and “methacrylate”, and to indicate one or both of “acrylamide” and “methacrylamide”. May be written as “(meth) acrylamide”, and may be written as “(meth) acryloxy” to indicate one or both of “acryloxy” and “methacryloxy”.

<1. Photosensitive composition>
The photosensitive composition according to the present invention is a composition comprising a polyester amide acid (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C).

The preferred composition ratio of the polyester amic acid (A), the epoxy group-containing copolymer (B), and the 1,2-quinonediazide compound (C) is that of the polyester amic acid (A) and the epoxy group-containing copolymer (B). In the total amount of 100% by weight, the content of the epoxy group-containing copolymer (B) is 20 to 90% by weight, based on the total amount of 100 parts by weight of the polyester amic acid (A) and the epoxy group-containing copolymer (B). 1,2-quinonediazide compound (C) is 5 to 40 parts by weight.

In addition, the photosensitive composition concerning this invention may further contain other components other than the above in the range in which the effect of this invention is acquired.

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

The polyester amic acid (A) can be obtained by reacting the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3) as essential components. In that case, in Formula (1) and Formula (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 the diamine (a2), and R ⁴ is a residue obtained by removing two —OH from the polyvalent hydroxy compound (a3).

At least a solvent is required for the synthesis of the polyester amide acid (A). The photosensitive composition may be produced by using a liquid or gel polyester amic acid solution in consideration of handling properties while leaving the solvent as it is, and considering the transportability by removing this solvent. You may manufacture a photosensitive composition using solid-state polyester amic acid.

In addition, the synthesis of the polyester amide acid (A) may contain other compounds than the above as long as the object of the present invention is not impaired. Examples of other raw materials include a monohydroxy compound and a monoamine having an alkoxysilyl group.

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

Examples of preferred compounds of the compound (a1) having two or more acid anhydride groups include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and anhydrous Mention may be made of copolymers of maleic acid and other compounds.

As a specific example of the compound (a1) having two or more acid anhydride groups, the compound used in the Examples is preferably an aromatic tetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as “ODPA”) and aliphatic tetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride (hereinafter “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 above-described compound, 3,3 ′, 4,4′-benzophenone tetra which is an aromatic tetracarboxylic dianhydride Carboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Diphenylsulfonetetracarboxylic dianhydride, 2,2', 3,3'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylsulfonetetracarboxylic 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); cycloaliphatic tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentane Mention may be made of tetracarboxylic dianhydride and cyclohexanetetracarboxylic dianhydride; and ethanetetracarboxylic dianhydride which is an aliphatic tetracarboxylic dianhydride. Among the specific examples of the compound (a1) having the above, at least one kind can be used.

Among the specific examples of the compound (a1) having two or more of these acid anhydride groups, polyester amide acid (which is easily available and has good compatibility with the epoxy group-containing copolymer (B) ( Examples of the compound that gives A) include 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, ODPA, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride. , BT-100, ethylene glycol bis (anhydrotrimellitate), and styrene-maleic anhydride copolymer are more preferable, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, ODPA , BT-100, and styrene-maleic anhydride copolymer are particularly preferred.

As specific examples of commercially available styrene-maleic anhydride copolymers, SMA 3000P (molar ratio of styrene / maleic anhydride: 3, weight average molecular weight 9,500, number average molecular weight 3,800), SMA 2000P (styrene / anhydride) Maleic acid molar ratio: 2, weight average molecular weight 7,500, number average molecular weight 3,000), and SMA 1000P (styrene / maleic anhydride molar ratio: 1, weight average molecular weight 5,500, number average molecular weight 2,000) ) (All are trade names; Kawa Crude Oil Co., Ltd., values are listed in the catalog). Calculating from the styrene / maleic anhydride molar ratio and number average molecular weight listed 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 per molecule of SMA1000P The average carbon number is 120.

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

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

As a specific example of the diamine (a2), 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as “DDS”), which is a diamine having two benzene rings, is preferably used in the examples. Can do.

As specific examples of the diamine (a2), in addition to the above-mentioned compounds, 4,4′-diaminodiphenylsulfone and 3,4′-diaminodiphenylsulfone, which are diamines having two benzene rings; Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, and 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Among specific examples of the amine (a2), it is possible to use at least one.

Among the specific examples of these diamines (a2), DDS is a compound that gives polyester amic acid (A) that is easily available and has good compatibility with the epoxy group-containing copolymer (B). And bis [4- (3-aminophenoxy) phenyl] sulfone are more preferred, and DDS is particularly preferred.

<1-1-3. Polyvalent hydroxy compound (a3)>
In the present invention, the polyvalent hydroxy compound (a3) is used as a raw material for obtaining the polyester amic acid (A).

式（Ｈ−１）において、Ｒ^１０１は単結合又は炭素数１〜１０の有機基であり；

式（Ｈ−２）において、Ｒ^１０２は炭素数１〜１０の有機基である。 Examples of preferred compounds of the polyvalent hydroxy compound (a3) include aliphatic diols, compounds represented by the following formula (H-1), compounds represented by the following formula (H-2), and polyisocyanates having an isocyanuric ring. Mention may be made of monohydric alcohols.

In the formula (H-1), R ¹⁰¹ is a single bond or an organic group having 1 to 10 carbon atoms;

In the formula (H-2), R ¹⁰² is an organic group having 1 to 10 carbon atoms.

A specific example of the polyvalent hydroxy compound (a3) is preferably 1,4-butanediol, which is an aliphatic diol, which is the compound used in the examples.

As specific examples of the polyvalent hydroxy compound (a3), in addition to the aforementioned compounds, aliphatic diols such as ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol and 1,8-octanediol; 2,2-bis (4-hydroxycyclohexyl) propane and 4,4′-dihydroxydicyclohexyl which are compounds represented by the formula (H-1); 2-Hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2- (4-hydroxyphenyl) ethanol which are compounds represented by (H-2); and isocyanuric acid tris (2- Hydroxyethyl) and the polyvalent hydroxy compound ( Among specific examples of 3), it is possible to use at least one.

Among the specific examples of these polyvalent hydroxy compounds (a3), compounds that are easily available and give polyester amic acid (A) having good compatibility with the epoxy group-containing copolymer (B) 1,4-butanediol and 1,6-hexanediol are more preferable, and 1,4-butanediol is particularly preferable.

<1-1-4. Monohydroxy Compound>
The raw material of the polyester amic acid (A) may contain other raw materials other than those described above as necessary within the range not impairing the object of the present invention, and examples of other raw materials include monohydroxy compounds. be able to.

式（Ｈ−３）において、Ｒ^１０３〜Ｒ^１０６はそれぞれ独立に水素又はメチル基であり、Ｒ^１０７は炭素数１〜１０の有機基であり、ｍは１〜１０の整数である。 Examples of preferable compounds of the monohydroxy compound include aliphatic monoalcohols, compounds represented by the following formula (H-3), alicyclic monoalcohols, and aromatic monoalcohols.

In Formula (H-3), R ^{103 to} R ¹⁰⁶ are each independently hydrogen or a methyl group, R ¹⁰⁷ is an organic group having 1 to 10 carbon atoms, and m is an integer of 1 to 10.

As a specific example of the monohydroxy compound, benzyl alcohol, which is a compound used in the examples and is an aromatic monoalcohol, is preferable.

As specific examples of the monohydroxy compound, in addition to the above-described compounds, isopropyl alcohol, which is an aliphatic monoalcohol; benzyl alcohol, propylene glycol monoethyl ether, which is a compound represented by the formula (H-3) , 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-hydroxymethyl Oxetane; and dimethylbenzyl carbinol, an aromatic monoalcohol.

Among the specific examples of these monohydroxy compounds, benzyl alcohol is a compound that can be easily obtained and gives polyester amic acid (A) having good compatibility with the epoxy group-containing copolymer (B). , Propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable, and benzyl alcohol is particularly preferable.

When a monohydroxy compound is used as the raw material of the polyester amic acid (A), the amount of the monohydroxy compound used is the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3). ) Is preferably 100 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight as a total.

<1-1-5. Monoamine having alkoxysilyl group>
The synthesis of the polyester amic acid (A) may contain other raw materials other than those described above as necessary, as long as the object of the present invention is not impaired, and has an alkoxysilyl group as an example of the other raw materials. Mention may be made of monoamines.

Specific examples of the monoamine having an alkoxysilyl group used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4 -Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p- Mention may be made of aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. Of these, at least one can be used.

Among the specific examples of monoamines having these alkoxysilyl groups, compounds that are easy to obtain and give polyester amic acid (A) having good compatibility with the epoxy group-containing copolymer (B) 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable.

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

<1-1-6. Solvent used for the synthesis reaction of polyester amic acid (A)>
Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amic acid (A) include methyl 3-methoxypropionate (hereinafter abbreviated as “MMP”), ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol methyl. Examples include 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. Synthesis Method of Polyesteramide Acid (A)>
The method for synthesizing the polyester amic acid (A) used in the present invention comprises the above synthesis using the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3) as essential raw materials. The reaction is carried out in the solvent used for the reaction.

The preferred raw material ratio of the polyester amic acid (A) is that X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric hydroxy compound are represented by the formulas (3) and (4). This is the ratio. If it is this range, the solubility to the solvent of polyester amide acid (A) is high, and the applicability | paintability to the base material of a photosensitive composition is favorable.

In the formula (3), preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. 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 the polyester amic acid (A), an acid anhydride group (—CO—O—CO—) is present at the terminal under the condition where X is excessively used with respect to Y + Z within the range of the above formula (4). It is thought that molecules are generated in excess of molecules having an amino group or a hydroxyl group at the terminal. On the other hand, when reacting in such a monomer structure, when a monohydroxy compound and a monoamine having an alkoxysilyl group are added, it reacts with an acid anhydride group at the end of the molecule to esterify and amidate, respectively. it can. The polyester amic acid (A) obtained by adding and reacting a monohydroxy compound further improves the coatability of the photosensitive composition, and is obtained by adding and reacting a monoamine having an alkoxysilyl group. The amic acid (A) can improve the adhesion between the cured film and the substrate.

When the solvent used in the synthesis reaction is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3), the reaction Is preferable because it proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

The order of adding the raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a compound (a1) having two or more acid anhydride groups, a diamine (a2), and a polyvalent hydroxy compound (a3) to a reaction solvent, a diamine (a2) and a polyvalent hydroxy compound (a3) After dissolving in a reaction solvent, a method of adding a compound (a1) having two or more acid anhydride groups, a compound (a1) having two or more acid anhydride groups and a polyvalent hydroxy compound (a3) are reacted in advance. Then, a method of adding the diamine (a2) to the solution containing the reaction product, or reacting the compound (a1) having two or more acid anhydride groups and the diamine (a2) in advance, and the reaction product Any technique such as a technique of adding a polyvalent hydroxy compound (a3) to a solution containing a product can be used.

When the monohydroxy compound is reacted, it may be added at any point in the reaction.

When the monoamine having an alkoxysilyl group is reacted, after the reaction of the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyvalent hydroxy compound (a3), the reaction product is included. After cooling the solution to 40 ° C. or lower, a monoamine having an alkoxysilyl group may be added and reacted at 10 to 40 ° C. for 0.1 to 6 hours.

The polyester amide acid (A) synthesized as described above includes a structural unit represented by the formula (1) and a structural unit represented by the formula (2), and the terminal thereof is an acid anhydride group as a raw material. An acid anhydride group derived from any one of a compound (a1), a diamine (a2), a polyvalent hydroxy compound (a3), a monohydroxy compound, and a monoamine having an alkoxysilyl group, an amino group, It is comprised by additives other than a hydroxy group, an alkoxy silyl group, or these compounds.

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, the applicability | paintability to the base material of a photosensitive composition will be 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. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

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

At least a solvent is required for the synthesis of the epoxy group-containing polymer (B). The photosensitive composition may be produced by using a liquid or gel-like epoxy group-containing polymer solution in consideration of handling properties while leaving the solvent as it is. You may manufacture a photosensitive composition using the solid epoxy group containing polymer considered.

<1-2-1. Polymerizable compound having epoxy group (b1)>
In this invention, the polymeric compound (b1) which has an epoxy group is used as a raw material for obtaining an epoxy group containing copolymer (B).

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

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 preferably include glycidyl methacrylate used in the examples.

Specific examples of the polymerizable compound (b1) having an epoxy group include glycidyl acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexyl (meth) acrylate in addition to the above-described compounds. Of the above-described specific examples of the polymerizable compound (b1) having an epoxy group, at least one kind can be used.

Among the specific examples of the polymerizable compound (b1) having these epoxy groups, an epoxy group-containing copolymer (B) that is easily available and has good compatibility with the polyester amic acid (A) is used. As the compound to be provided, glycidyl (meth) acrylate is more preferable, and glycidyl methacrylate is particularly preferable.

<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 the 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 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 essentially contains a polymerizable compound having a phenolic hydroxyl group as the polymerizable compound (b2).

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

As an example of the preferable compound of the polymeric compound which has a phenolic hydroxyl group, the compound represented by Formula (5) and the compound represented by Formula (6) can be mentioned.

As specific examples of the polymerizable compound having a phenolic hydroxyl group, 4-hydroxystyrene and 4-hydroxyphenyl vinyl ketone, which are compounds used in the examples and represented by the formula (5), and The 4-hydroxyphenyl methacrylate which is a compound represented by Formula (6) can be mentioned.

As specific examples of the polymerizable compound having a phenolic hydroxyl group, 2-hydroxystyrene, 3-hydroxystyrene, 2-hydroxymethylstyrene, which is a compound represented by the formula (5), in addition to the aforementioned compound, 3-hydroxymethylstyrene, 4-hydroxymethylstyrene, 2-hydroxyphenyl vinyl ketone, and 3-hydroxyphenyl vinyl ketone; and 2-hydroxyphenyl (meth) acrylate, which is a compound represented by formula (6), 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl (meth) acrylamide, 3-hydroxyphenyl (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide, 4-hydroxybenzyl (meth) acrylate , 4-hydroxyphenylethyl (meth) acrylate, and 4-hydroxyphenyloxyethyl (meth) acrylate, and at least one of the above-described specific examples of the polymerizable compound having a phenolic hydroxyl group should be used. Can do.

Among the specific examples of the polymerizable compound having a phenolic hydroxyl group, a compound which is easily available and gives an epoxy group-containing copolymer (B) having good compatibility with the polyester amide acid (A) As 4-hydroxystyrene, 4-hydroxymethylstyrene, 4-hydroxyphenyl vinyl ketone, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide, and 4-hydroxyphenyloxyethyl (meth) acrylate Are more preferable, and 4-hydroxystyrene, 4-hydroxyphenyl vinyl ketone, and 4-hydroxyphenyl (meth) acrylate are particularly preferable.

<1-2-2-2. Among polymerizable compounds (b2), a polymerizable compound having no phenolic hydroxyl group>
Of the polymerizable compound (b2), specific examples of the compound having no phenolic hydroxyl group are preferably methacrylic acid, benzyl methacrylate, and N-cyclohexylmaleimide used in the examples.

Of the polymerizable compounds (b2), specific examples of polymerizable compounds having no phenolic hydroxyl group include acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) in addition to the above-described compounds. ) Acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, tert-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, 2- (i- Propoxy) ethyl (meth) acrelane 2- (n-butoxy) ethyl (meth) acrylate, 2- (i-butoxy) ethyl (meth) acrylate, 2- (sec-butoxy) ethyl (meth) acrylate, 2- (tert-butoxy) ethyl (meth) ) Acrylate, 2-phenoxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, 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-trimethoxysilylpropyl (meth) acrylate, and 3-triethoxysilylpropyl (meth) acrylate, styrene, methylstyrene, N-phenyl A maleimide can be mentioned, Among the polymerizable compounds (b2), at least one of specific examples of compounds not represented by any of the formulas (5) and (6) can be used.

Among these polymerizable compounds (b2), among specific examples of polymerizable compounds having no phenolic hydroxyl group, an epoxy group that is easily available and has good compatibility with the polyester amic acid (A) Examples of compounds that give the copolymer (B) are n-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and mono (meth) acrylic. Roxypropyl-modified polydimethylsiloxane, 3- [tris (trimethylsilyloxy) silyl] propyl (meth) acrylate, styrene, N-cyclohexylmaleimide, and N-phenylmaleimide are more preferred, and n-butyl (meth) acrylate, benzyl (meth) ) Acrylate, disic Pentenyl oxyethyl (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, N- cyclohexyl maleimide, and N- phenylmaleimide is particularly preferred.

Of these polymerizable compounds (b2), among the specific examples of polymerizable compounds having no phenolic hydroxyl group, they are easily available and when the epoxy group-containing copolymer (B) is produced. Compounds that give good solubility in the developer include (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-trimethoxysilylpropyl (meth) acrylate. More preferred are (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate.

<1-2-3. Solvent used for polymerization reaction of epoxy group-containing copolymer (B)>
Specific examples of the solvent used in the polymerization reaction for obtaining the epoxy group-containing copolymer (B) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, and butyl methoxyacetate. , Methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, MMP, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate , Methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, pyrubin Ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 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 acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether preferable.

<1-2-4. Polymerization Method of Epoxy Group-Containing Copolymer (B)>
The method for polymerizing the epoxy group-containing copolymer (B) used in the present invention comprises a polymerizable compound (b1) having an epoxy group and a polymerizable compound having a phenolic hydroxyl group as essential raw materials and a solvent used for the polymerization reaction. React in.

The preferable raw material ratio of the epoxy group-containing copolymer (B) is such that the polymerizable compound having an epoxy group is 20 to 90 in a total amount of 100% by weight of the polymerizable compound (b1) and the polymerizable compound (b2) having an epoxy group. The polymerizable compound having a phenolic hydroxyl group is 1 to 40% by weight. If it is this range, the line pattern shape linearity at the time of short time image development of the photosensitive composition will be especially favorable.

The solvent used for the polymerization reaction is preferably 100 parts by weight or more 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, because the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

The polymerization method of the epoxy group-containing polymer (B) is not particularly limited, but radical polymerization in a solution using a solvent is preferable. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, but is usually in the range of 50 to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out 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 is a compound having at least one 1,2-quinonediazide group in one molecule.

The 1,2-quinonediazide compound (C) is suitable for use because a condensate of a compound having a phenolic hydroxyl group and a sulfonic acid 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, tri (p-hydroxyphenyl) methane, 1,1,1-tri (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] ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxy A flavan can be mentioned.

Specific examples of the sulfonic acid chloride having a 1,2-quinonediazide group include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

Specific examples of these compounds having a phenolic hydroxyl group and specific examples of 1,2-quinonediazide compounds (C) using specific examples of sulfonic acid chlorides having a 1,2-quinonediazide group are preferably used in the examples. 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride condensate be able to.

As a 1,2-quinonediazide compound (C) using specific examples of these compounds having a phenolic hydroxyl group and a specific example of a sulfonic acid chloride having a 1,2-quinonediazide group, it is easily available and polyester amic acid Compounds having good compatibility with (A) include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2 ′ -Condensates of naphthoquinonediazide-4-sulfonic acid chloride, and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2- A condensate of naphthoquinonediazide-5-sulfonic acid chloride is more preferable, and 4,4 ′-[1- [4- [1- [4-hydro Shifeniru] -1-methylethyl] phenyl] ethylidene] condensate of bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is particularly preferred.

<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, curability, and UV degradation 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 An epoxy compound other than an antioxidant such as a compound, an epoxy curing agent, an ultraviolet absorber, an aggregation inhibitor, a thermal crosslinking agent, and an epoxy group-containing copolymer (B) is mainly exemplified.

<1-4-1. Surfactant>
In order to improve the 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, 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 (all trade names; 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 Mention may be made of sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

Among specific examples of 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 , Fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylsulfonate, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonate At least one type is preferable because the coating uniformity of the photosensitive composition is increased.

The surfactant content 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>
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 the adhesion between the formed cured film and the substrate is improved.

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

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 photosensitive composition of this invention. Among these, a hindered phenol type is preferable 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.

<1-4-4. Epoxy curing agent>
The photosensitive composition of the present invention may further contain an epoxy curing agent in order to improve curability. 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 thermosensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent is preferable from a compatible viewpoint with a polyester amide acid (A).

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 anhydride and hexahydrotrimellitic anhydride that can improve curability 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 may be mentioned. Among these, 2-undecylimidazole that can improve curability without impairing the solubility of the photosensitive composition in the solvent is particularly preferable.

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

<1-4-5. UV absorber>
The photosensitive composition of the present invention may contain 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, 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.

<1-4-6. Anti-agglomeration agent>
The photosensitive composition of the present invention may contain an agglomeration inhibitor from the viewpoint of allowing the solid content to blend with the solvent and preventing agglomeration.

Specific examples of the aggregation inhibitor include Disperbak-145, Disperbak-161, Dispersake-162, Dispersake-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 , FT 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.

<1-4-7. Thermal crosslinking agent>
The photosensitive composition of the present invention may contain a thermal crosslinking agent from the viewpoint of further improving curability and heat resistance.

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.

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

Epoxy compounds other than the epoxy group-containing copolymer (B) are used by adding 0.1 to 50 parts by weight to 100 parts by weight of the total amount of the polyester amic acid (A) and the epoxy group-containing copolymer (B). .

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, biphenyl type epoxy compounds, phenol novolac type epoxy compounds, cresol novolak type. Mention may be made of epoxy compounds, bisphenol A novolac epoxy compounds, and alicyclic epoxy compounds.

Specific examples of commercially available bisphenol A type epoxy compounds include jER 828, 1004, and 1009 (all trade names: Mitsubishi Chemical Corporation); specific examples of commercially available bisphenol F type epoxy compounds include jER. 806, 4005P (both trade names; Mitsubishi Chemical Corporation) can be mentioned; specific examples of commercially available glycidyl ether type epoxy compounds include Techmore VG3101L (trade name; Printec Co., Ltd.), EPPN-501H, 502H. (All trade names; Nippon Kayaku Co., Ltd.), jER 1032H60 (trade names; Mitsubishi Chemical Corporation); specific examples of commercially available biphenyl type epoxy compounds include jER YX4000, YX4000H, YL6121H (any Product name; Mitsubishi Chemical Corporation Specific examples of commercially available phenol novolac epoxy compounds include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), jER 152, 154 (both trade names: Mitsubishi Chemical Corporation). Specific examples of commercially available cresol novolak type epoxy compounds include EOCN-102S, 103S, 104S, and 1020 (all trade names: Nippon Kayaku Co., Ltd.); commercially available bisphenol A novolaks. Specific examples of the epoxy compound include jER 157S65 and 157S70 (both trade names; Mitsubishi Chemical Corporation); specific examples of commercially available alicyclic epoxy compounds include Celoxide 2021P and EHPE-3150 ( Both can be listed as trade names; Daicel Corporation) . Note that Techmore 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-epoxypropoxy) phenyl] -1- [4- [1- [4- (2 , 3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol.

<1-5. Solvent optionally added to the photosensitive composition>
A solvent may be added to the photosensitive composition of the present invention in addition to the solvent used for the synthesis reaction of the polyester amic acid (A) and the solvent used for the polymerization reaction of the epoxy group-containing copolymer (B). Solvents optionally added to the photosensitive composition of the present invention (hereinafter referred to as “dilution solvent”) are polyester amic acid (A), epoxy group-containing copolymer (B), and 1,2-quinonediazide compound. A solvent capable of dissolving (C) and the like is preferable. Specific examples of the solvent for dilution include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxybutyl acetate. , Methyl 3-oxypropionate, ethyl 3-hydroxypropionate, MMP, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, 2-hydroxypropionic acid Propyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate , Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, Ethyl acetoacetate, 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 acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Examples include diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. One type can be used.

<1-6. Storage of photosensitive composition>
When the photosensitive composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the composition has good stability over time, which is preferable. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

<2. Cured film of photosensitive composition>
The photosensitive composition of the present invention comprises a polyester amide acid (A), an epoxy group-containing copolymer (B), a 1,2-quinonediazide compound (C), and an additive, and further a diluent solvent is selected as necessary. And then uniformly mixing and dissolving them. As the additive, a coupling agent, a surfactant, and other additives can be selected and used as necessary depending on the intended properties.

When the photosensitive composition (after being dissolved in a solvent in the case of a solid state without a solvent) prepared as described above is applied to the surface of the substrate and the solvent is removed by, for example, heating, the coating film is formed. Can be formed. 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 or an oven. 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 1,000 mJ / cm ^{2 for} i-line. The photosensitive composition in the part irradiated with ultraviolet rays is solubilized in an alkali developer by improving the alkali solubility of the 1,2-quinonediazide compound.

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 reacts with the epoxy group-containing copolymer (B) to increase the molecular weight, it is very tough and has excellent heat 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 the TFT and the transparent electrode or an insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Furthermore, the cured film of the present invention is effective even when used as a protective film for LED light emitters.

Next, the present invention will be specifically described with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples.

The compounds used in Reference Synthesis Examples, Synthesis Examples, Comparative Synthesis Examples, Reference Examples, Examples, and Comparative Examples are described for each component.

Among the compounds (a1) having two or more acid anhydride groups, tetracarboxylic dianhydride:
a1-1: ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride a1-2: BT-100: 1,2,3,4-butanetetracarboxylic dianhydride group Of the compounds (a1) having two or more, styrene-maleic anhydride copolymer:
a1-3: Trade name SMA-1000P, Sartomer Co., Ltd.
a2-1: DDS: 3,3′-diaminodiphenylsulfone polyvalent hydroxy compound (a3):
a3-1: 1,4-butanediol monohydroxy compound:
a4-1: Benzyl alcohol
Solvent used for the synthesis reaction of the polyester amic acid (A):
MMP: methyl 3-methoxypropionate PGMEA: propylene glycol monomethyl ether acetate

Polymerizable compound (b1) having an epoxy group:
b1-1: Among glycidyl methacrylate and other polymerizable compounds (b2), a polymerizable compound having a phenolic hydroxyl group:
b2-1: 4-hydroxystyrene b2-2: 4-hydroxyvinyl ketone b2-3: 4-hydroxyphenyl methacrylate Polymeric compound having no phenolic hydroxyl group among other polymerizable compounds (b2):
b2-4: Methacrylic acid b2-5: Benzyl methacrylate b2-6: Polymerization initiator used for the polymerization reaction of the N-cyclohexylmaleimide epoxy group-containing copolymer (B):
2,2′-azobis (2-methylpropionic acid) dimethyl (trade name V-601, Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as “V-601”)
Solvent used for the polymerization reaction of the epoxy group-containing copolymer (B):
PGMEA: Propylene glycol monomethyl ether acetate

1,2-quinonediazide compound (C):
4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride condensate (average ester Conversion rate 58%, abbreviated as "PAD")

Dilution solvent:
PGMEA: Propylene glycol monomethyl ether acetate

Additive-1: 3-glycidyloxypropyltrimethoxysilane which is a silane coupling agent (trade name; Silaace S510, JNC Corporation, hereinafter abbreviated as “S510”)
Additive-2: Megafac F-556 (trade name, DIC Corporation, hereinafter abbreviated as “F-556”), which is a fluorochemical surfactant

A polyester amic acid solution containing reaction products such as tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below (Synthesis Examples 1 and 2).

[Synthesis Example 1] Synthesis of polyester amic acid solution (A1) Thermometer, stirrer, raw material charging charge port and nitrogen gas inlet port A 1,000 mL four-necked flask was charged with 446 MMP as a solvent used in the synthesis reaction. .96 g, 31.93 g of 1,4-butanediol as a polyhydroxy compound, 25.54 g of benzyl alcohol as a monohydroxy compound, 183.20 g of ODPA as a tetracarboxylic dianhydride, and 130 ° C. in a dry nitrogen stream For 3 hours. Thereafter, the solution after the reaction was cooled to 25 ° C., 29.33 g of DDS and 183.04 g of MMP were added as diamines, stirred at 20-30 ° C. for 2 hours, then stirred at 115 ° C. for 1 hour, 30 ° C. or less. Was cooled to a 30% by weight solution (A1) of a pale yellow transparent polyester amide acid. The weight average molecular weight measured by GPC was 4,200.

[Z / Y = 3, (Y + Z) /X=0.8]

Here, the “polyesteramide acid 30% by weight solution (A1)” means that the concentration calculated from the weight of the solid and the weight of the solvent calculated as all the compounds charged as described above is 30. Represents weight percent. The following synthesis examples and comparative synthesis examples are also the same.

[Synthesis Example 2] Polyesteramide acid solution (A2) synthesis thermometer, stirrer, raw material charging charge port, and nitrogen gas introduction port, 1,000 mL four-necked flask, PGMEA 604 as a solvent used for the synthesis reaction .80 g, 34.47 g of BT-100 as a tetracarboxylic dianhydride, 164.11 g of SMA-1000P as a styrene-maleic anhydride copolymer, 50.17 g of benzyl alcohol as a monohydroxy compound, a polyvalent carboxyl compound As a starting material, 10.45 g of 1,4-butanediol was charged and stirred at 130 ° C. for 3 hours under a dry nitrogen stream. Thereafter, the solution after the reaction was cooled to 25 ° C., 10.80 g of DDS and 25.20 g of PGMEA were added as diamines, stirred at 20-30 ° C. for 2 hours, then stirred at 115 ° C. for 1 hour, 30 ° C. or less. To give a 30% by weight solution (A2) of a pale yellow transparent polyester amide acid. 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 containing a reaction product of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) was synthesized as shown below (Synthesis Examples 3 to 12 and Comparative Synthesis Example 1). ~ 2).

[Synthesis Example 3] Synthesis of epoxy group-containing copolymer solution (B1) In a four-necked flask with a stirrer, PGMEA as a solvent used for the polymerization reaction, glycidyl methacrylate as the polymerizable compound (b1) having an epoxy group, and the like Among the polymerizable compounds (b2), 4-hydroxystyrene as a polymerizable compound having a phenolic hydroxyl group, and methacrylic acid and benzyl methacrylate as polymerizable compounds having no phenolic hydroxyl group among other polymerizable compounds (b2) As a polymerization initiator, V-601 was charged with the following composition, heated at 80 ° C. for 3 hours, and then heated at 90 ° C. for 1 hour.
Glycidyl methacrylate 70.80g
4-hydroxystyrene 4.80g
Methacrylic acid 8.40g
Benzyl methacrylate 36.00g
V-601 18.00g
PGMEA 280.00g
The solution after completion of the polymerization reaction was cooled to room temperature to obtain a 30 wt% solution (B1) of an epoxy group-containing copolymer. The weight average molecular weight determined by GPC analysis was 17,000.

[Synthesis Examples 4 to 10, Reference Synthesis Examples 1 to 3, and Comparative Synthesis Examples 1 to 2]
According to the method of Synthesis Example 3, an epoxy group-containing copolymer solution was obtained by performing a polymerization reaction using each component as a raw material at a ratio (unit: g) described in Table 1. The weight average molecular weight of the resulting epoxy group-containing copolymer is also shown in Table 1.

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

The total amount of the solvent contained in the composition is the total amount of MMP contained in the polyester amic acid solution (A1), PGMEA contained in the epoxy group-containing copolymer solution (B′1), and the dilution solvent PGMEA. In this step, the solid content concentration was adjusted to about 28% by weight. The same applies to Reference Example 2 and below, 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, using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) through a mask having a line pattern with a width of 50 μm in the air, light of 350 nm or less is cut through a wavelength cut filter. The g, h and i lines were taken out and exposed. The exposure dose was 200 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name; Ushio Corporation) and a photoreceiver UVD-365PD (trade name: Ushio Corporation). The exposed coating film was subjected to paddle development for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution, then the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. Furthermore, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain a glass substrate with a cured film having a line pattern with a film thickness of 3.0 μm and a pattern width of approximately 50 μm.

[Evaluation method of heat resistance]
The glass substrate with a cured film having the obtained line pattern was reheated at 240 ° C. for 1 hour, and then the film thickness before heating and the film thickness after heating were measured, and the remaining film ratio was calculated by the following formula. For measuring 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 remaining film ratio after heating was 95% or more was evaluated as “◯”, and a case where the remaining film ratio after heating was less than 95% was evaluated as “×”.

Residual film ratio = (film thickness after heating / film thickness before heating) × 100%

[Confirmation method of undulation of 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 undulations in the line pattern shape was confirmed. FIG. 1 shows a state where the line pattern shape is not wavy, and FIG. 2 shows a state where the line pattern shape is wavy.

[Reference Examples 2-3]
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 heat resistance using the photosensitive compositions of Reference Examples 2 to 3 and the results of confirming whether or not the line pattern shape is wavy.

[Examples 1-8 and Comparative Examples 1-2]
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.

Using these photosensitive compositions obtained, a glass substrate with a cured film having a line pattern with a pattern width of about 50 μm was obtained according to the method of Reference Example 1. However, in the method of Reference Example 1, the time of the development process in which the paddle development was performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution was changed from 60 seconds to 30 seconds.

Using the obtained glass substrate with a cured film having a line pattern, the heat resistance was evaluated and the presence or absence of undulations in the line pattern shape was confirmed according to the method of Reference Example 1. The results are shown in Table 2.

[Line pattern shape linearity evaluation method during short-time development]
In Examples 1 to 8 and Comparative Examples 1 and 2 in which the development process time is 30 seconds, the line pattern shape linearity during short-time development is ○, The line pattern shape linearity during short-time development was evaluated as x.

Reference Example 1, which is a photosensitive composition that does not contain a polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy group-containing copolymer (B) under the condition that the development process time is 60 seconds, and contains an epoxy group A difference is not seen between the reference examples 2-3 which are the photosensitive compositions containing the polymeric compound which has a phenolic hydroxyl group in the raw material of a copolymer (B).

Comparative Example 1 which is a photosensitive composition that does not contain a polymerizable compound having a phenolic hydroxyl group in the raw material of the epoxy group-containing copolymer (B) under the condition that the development time is shortened to 30 seconds is a line pattern shape The problem of the occurrence of undulations was observed. However, Examples 1 to 8, which are photosensitive compositions containing a polymerizable compound having a phenolic hydroxyl group as a raw material for the epoxy group-containing copolymer (B), do not have the problem of occurrence of undulations in the line pattern shape. .

Examples 1 to 8 are developed in a short time in a situation where a reduction in the manufacturing process time is required from the result under the condition that the development process time is 60 seconds and the result under the condition that the development process time is 30 seconds. There was a clear advantage in the linearity of the time line pattern.

Moreover, it turns out that the comparative example 2 which is a photosensitive composition which does not contain a polyester amide acid (A) is inferior in heat resistance.

The cured film obtained from the photosensitive composition of the present invention has high heat resistance and excellent line pattern shape linearity at the time of short-time development, so that various optics such as a color filter, an LED light emitting element, and a light receiving element are used. It can be used as a protective film such as a material, and an insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (7)

A photosensitive composition comprising a polyester amic acid (A), an epoxy group-containing copolymer (B) and a 1,2-quinonediazide compound (C);
The polyester amide 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 a copolymer of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) other than (b1); and
The polymerizable compound (b2) is a photosensitive composition containing a polymerizable compound having a phenolic hydroxyl group.

In Formula (1), R ¹ is an organic group having 2 to 1000 carbon atoms, and R ² is an organic group having 2 to 100 carbon atoms;

In Formula (2), R ³ is an organic group having 2 to 1000 carbon atoms, and R ⁴ is an organic group having 2 to 100 carbon atoms. The structural unit represented by the formula (1) is a structural unit made from a compound (a1) having two or more acid anhydride groups and a diamine (a2) as raw materials;
The photosensitive unit according to claim 1, wherein the structural unit represented by the formula (2) is a structural unit made from a compound (a1) having two or more acid anhydride groups and a polyvalent hydroxy compound (a3) as raw materials. Sex composition. The compound (a1) having two or more acid anhydride groups is one or more compounds selected from a tetracarboxylic dianhydride and a styrene-maleic anhydride copolymer;
The polyester amic acid (A) is composed of X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyhydric hydroxy compound, and the following formulas (3) and (4) are satisfied. The photosensitive composition of Claim 2 which is a reaction material of the raw material included in such a ratio.

0.2 ≦ Z / Y ≦ 8.0 (3)
0.2 ≦ (Y + Z) /X≦5.0 (4) The polymerizable compound (b1) having an epoxy group is one or more selected from (meth) acrylates having an epoxy group;
The photosensitive composition according to claim 1, wherein the polymerizable compound having a phenolic hydroxyl group is one or more selected from a compound represented by the following formula (5) and a compound represented by the following formula (6). object.

In Formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbon atoms, R ⁶ is a single bond or —C (═O) —, and R ^{7 to} R ¹¹ are each independently a hydroxyl group or It is a C1-C7 organic group. Provided that 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 divalent having 1 to 40 carbon atoms. It is an organic group, and R ^{15 to} R ¹⁹ are each independently a hydroxyl group or an organic group having 1 to 7 carbon atoms. However, at least one of R ^{15 to} R ¹⁹ is a hydroxyl group. The (meth) acrylate having an epoxy group is glycidyl (meth) acrylate;
The compound represented by the formula (5) is one or more selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenyl vinyl ketone;
The compound represented by the formula (6) is one or more selected from 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide, and 4-hydroxyphenyloxyethyl (meth) acrylate, The photosensitive composition of Claim 4. Of the total amount of 100% by weight of the polyester amic acid (A) and the epoxy group-containing copolymer (B), the content of the epoxy group-containing copolymer (B) is 20 to 90% by weight, and the polyester amic acid (A) The photosensitive composition according to claim 1, wherein the 1,2-quinonediazide compound (C) is 5 to 40 parts by weight relative to 100 parts by weight of the total amount of the epoxy group-containing copolymer (B). The cured film obtained from the photosensitive composition of any one of Claims 1-6.

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