TW201714966A - Photosensitive compositions and use thereof for producing a hardened film having excellent heat resistance, flatness, transparency, and resolvability - Google Patents

Abstract

The present invention relates to a photosensitive composition, which is a composition containing a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy hardener, and a molecular weight regulator. The photosensitive composition is characterized in that the polyester amide acid is originated from a reaction product of raw materials containing a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as the essential components. By using the photosensitive composition of the present invention, a hardened film having excellent heat resistance, flatness, transparency, and resolvability can be obtained.

Description

Photosensitive composition and its application

The present invention relates to an insulating material for forming an electronic component, a passivation film, a buffer coating film, an interlayer insulating film, or a planarization 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 such as a transparent film using the photosensitive composition, and an electronic component including the film.

In the manufacturing steps of an element such as a display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution may be performed, or when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, a surface protective film may be provided in order to prevent deterioration, damage, and deterioration of the surface of various elements. For these protective films, it is required to be able to withstand various characteristics of various treatments in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, flatness, light resistance, etc. are required. . In the current state of high performance such as high viewing angle, high-speed response, and high definition of display elements, when used as a color filter protective film, transparency, heat resistance, and flattening characteristics are desired. Improved materials.

The type of the curable composition for forming these protective films can be roughly distinguished from a photosensitive composition and a thermosetting composition. When the film is formed, the thermosetting composition is completely cured by high-temperature heating. Therefore, even if it is heated to a high temperature in the subsequent step, the amount of volatile components generated is small and the heat resistance is excellent. A thermosetting protective film material having such excellent properties has a polyester phthalic acid composition (for example, see Patent Document 1). However, the thermosetting composition cannot form a scribe line at the time of manufacturing the panel division, and a large amount of fine particles of the protective film are generated, so that a high degree of panel cleaning step is required thereafter.

On the other hand, the photosensitive composition contains a polymer or oligomer having a photopolymerizable group or a monomer and a photopolymerization initiator, and undergoes a chemical reaction due to energy of light represented by ultraviolet rays, and is hardened. The photosensitive composition can easily form a scribe line for manufacturing a panel division, for example, and therefore has advantages such as fines that do not cause a protective film, and conversely, compared with a protective film formed of a thermosetting composition. The heat resistance of the protective film formed of the usual photosensitive composition is insufficient.

In recent years, the demand for a protective film requiring heat resistance has been increasing, and the demand for a protective film requiring a fine pattern shape has been increasing. Thus, a photosensitive composition capable of forming a fine film having excellent heat resistance and forming a fine pattern can be obtained.

A photosensitive composition which can form a protective film having a very excellent heat resistance is a polyimine precursor composition (for example, refer to Patent Document 2) and a soluble polyimine composition (for example, refer to Patent Document 3) . However, even in any photosensitive composition, an organic solvent in which the obtained polyimide intermediate precursor composition or soluble polyimine composition is dissolved is also limited, and an organic solvent having a very high polarity is also required.

Examples of the organic solvent having a high polarity such as a solution of a polyimine precursor composition and a soluble polyimine composition include a pyrrolidone type, an anthraquinone type, a formamide type, an acetamide type, a phenol type, a tetrahydrofuran, and a second. Oxane, γ-butyrolactone, and the like.

In particular, when these photosensitive compositions are used as a color filter protective film, if these organic solvents having a high polarity are contained, the color filter layer penetrating into the substrate, for example, a pigment or a dye contained in a pixel, etc. The coloring material is eluted, so that it is difficult to produce a high quality display element.

In the case of using the photosensitive composition in the protective film of the color filter, there are Patent Document 4 and Patent Document 5. However, the inventors of the present invention want to form a protective film using the photosensitive composition described in these patent documents. As a result, the pattern formed is not satisfactory, and further improvement is desired.

In addition, the curable composition and the thermosetting composition are required to have excellent coatability on the base substrate. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2009-286787 (Patent Document 5)

[Problem to be Solved by the Invention] An object of the present invention is to provide a cured film which is particularly excellent in transparency, heat resistance, flatness, and resolution without requiring an organic solvent having high polarity, and a composition for providing the cured film. Further, an electronic component having the cured film is provided. [Technical means to solve the problem]

In order to solve the above problems, the inventors of the present invention have conducted intensive studies, and as a result, have found that the object can be attained by the following composition and a cured film obtained by curing the composition, thereby completing the present invention. The composition comprises a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy hardener, and a molecular weight modifier, and the polyester phthalic acid is composed of a tetracarboxylic dianhydride. It is obtained by the reaction of a compound of a diamine and a polyvalent hydroxy compound. The present invention includes the following constitutions.

[1] A photosensitive composition comprising a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent, and a molecular weight modifier; The photosensitive composition is characterized in that the polyester proline is derived from a tetracarboxylic dianhydride containing X mole and a diamine of Y molar in a ratio which is established by the relationship of the following formulas (1) and (2). And a reaction product of a raw material of a polyvalent hydroxy compound of Z-mol, having a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); and a compound having a polymerizable double bond is contained in each molecule Two or more polymerizable double bonds; the epoxy compound contains two to ten epoxy groups per molecule, and the weight average molecular weight is less than 3,000; and has a polymerizable double bond with respect to 100 parts by weight of the polyester glycine acid. The total amount of the compound is from 20 parts by weight to 300 parts by weight, the total amount of the epoxy compound is from 20 parts by weight to 200 parts by weight, and the content of the photopolymerization initiator is more than 5.0 times and less than 30% of the content of the molecular weight modifier. Double; 0.2≦Z/Y≦8.0 ····· · (1) 0.2 ≦ (Y + Z) /X≦5.0 ··· (2) In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is a two-NH ₂ removal from the diamine. The resulting residue, R ^{3 ,} is a residue obtained by removing two -OH from a polyvalent hydroxy compound.

[2] The photosensitive composition according to [1], wherein the molecular weight modifier is selected from the group consisting of mercaptans, xanthogens, quinones, and 2,4-diphenyl groups. One or more of -4-methyl-1-pentene.

[3] The photosensitive composition according to [1], wherein the molecular weight modifier is naphthoquinone.

[4] The photosensitive composition according to [1], wherein the molecular weight modifier is 2-hydroxy-1,4-naphthoquinone.

[5] The photosensitive composition according to any one of [1] to [4] wherein the raw material component of the polyester phthalic acid further comprises a monohydroxy compound.

[6] The photosensitive composition according to [5], wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl- One or more of 3-hydroxymethyloxetane.

[7] The photosensitive composition according to any one of [1] to [5] wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000.

[8] The photosensitive composition according to any one of [1] to [5] wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3 One or more of 4-butane tetracarboxylic dianhydride and ethylene glycol bis(hydrogen trimellitate).

[9] The photosensitive composition according to any one of [1] to [5] wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-amine) One or more of phenoxy)phenyl]indoles.

[10] The photosensitive composition according to any one of [1] to [5] wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentane Alcohol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl And one or more of tris(2-hydroxyethyl) isocyanurate.

[11] The photosensitive composition according to any one of [1] to [5] wherein the compound having a polymerizable double bond contains 50% by weight or more based on the total weight of the compound having a polymerizable double bond. Selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isomeric cyanuric acid ethylene oxide modified triacrylate, and polyacid modified (meth)acrylic acid oligomerization One or more of them.

[12] The photosensitive composition according to any one of [1] to [5] wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxy Cyclohexylmethyl ester, 1-methyl-4-(2-methyloxacyclopropyl)-7-oxabicyclo[4.1.0]heptane, 2-[4-(2,3-epoxypropane Oxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane with 1,3-bis[4 -[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1- Mixture of methylethyl]phenyl]ethyl]phenoxy]-2-propanol, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1 , 1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether, 1,3-bis(oxopropylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 One or more of 1,2-epoxy-4-(2-oxopropyl)cyclohexane adducts of 2-bis(hydroxymethyl)-1-butanol.

[13] The photosensitive composition according to any one of [1] to [5] wherein the photopolymerization initiator is selected from the group consisting of α-aminoalkylphenone, decylphosphine One or more of an oxide-based or oxime ester-based photopolymerization initiator.

[14] The photosensitive composition according to any one of [1] to [5] wherein the epoxy hardener is selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole More than one of them.

[15] The photosensitive composition according to any one of [1] to [5] wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenyl ether tetracarboxylic acid One or more of an anhydride and 1,2,3,4-butanetetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenylanthracene; the polyvalent hydroxy compound is 1,4-butanediol; The monohydroxy compound is benzyl alcohol; the compound having a polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid modified (meth)acrylic oligomer; The total weight of the initiator, the photopolymerization initiator contains 50% by weight or more of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzamide) Ketone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9-oxazol-3-yl]-, 1-(O-ethylindenyl) and One or more of 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-ethenylhydrazine); epoxy compound Is selected from 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl) ]ethyl]phenyl]propane with 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-( 2,3-epoxypropoxy) Mixture of phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and 2-[4-(2,3-epoxypropoxy)phenyl]-2 One or more of [4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane; the epoxy hardener is selected from the group consisting of trimellitic anhydride And one or more of 2-undecylimidazole; the molecular weight modifier is 2-hydroxy-1,4-naphthoquinone, and the content of the photopolymerization initiator is 5.0 times more than the content of the molecular weight modifier; The molecular weight modifier is contained in a 30-fold manner; and one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate is further contained as a solvent.

[16] A cured film obtained by the photosensitive composition according to any one of [1] to [15].

[17] A color filter using the cured film according to [16] as a protective film.

[18] A display element using the color filter according to [17].

[19] A solid-state imaging element using the color filter according to [17].

[20] A display element using the cured film according to [16] as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[21] A display element using the cured film according to [16] as a transparent insulating film formed between the transparent electrode and the alignment film.

[22] A light-emitting diode (LED) light-emitting body using the cured film according to [16] as a protective film. [Effects of the Invention]

The photosensitive composition of the preferred embodiment of the present invention is a material which does not require an organic solvent having a high polarity and can form a cured film which is particularly excellent in transparency, heat resistance, flatness, and resolution, and is used as a color display element. In the case of a color filter protective film, display quality and reliability can be improved. According to the above, the practicality is very high, and in particular, it is effective as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. Moreover, it can also be used as a protective film of various optical materials and a transparent insulating film.

1. Photosensitive composition The photosensitive composition of the present invention is a compound containing polyester phthalic acid, containing two or more polymerizable double bonds per molecule, a photopolymerization initiator, and is contained in each molecule. a composition of two to ten epoxy groups having an average weight molecular weight of less than 3,000, an epoxy hardener, and a molecular weight modifier derived from a tetracarboxylic dianhydride, a diamine And a reaction product of a raw material of a polyvalent hydroxy compound as an essential component, wherein the photosensitive composition is characterized in that the compound having a polymerizable double bond is 20 parts by weight to 300 parts by weight based on 100 parts by weight of the polyester phthalic acid. The epoxy compound is contained in an amount of from 20 parts by weight to 200 parts by weight, and the content of the photopolymerization initiator is more than 5.0 times and less than 30 times the content of the molecular weight modifier. Further, the photosensitive composition of the present invention may further contain other components than the above in the range in which the effects of the present invention are obtained.

1-1. Polyester phthalic acid The polyester phthalic acid in the present invention is a reaction product derived from a raw material containing tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential components. More specifically, the polyester proline is derived from a tetracarboxylic dianhydride containing X mole, a diamine of Y mole, and Z in a ratio established by the relationship of the following formulas (1) and (2). The reaction product of a raw material of a molar polyvalent hydroxy compound. 0.2≦Z/Y≦8.0 ·······(1)0.2≦(Y+Z)/X≦5.0 ···(2)

The polyester phthalic acid has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4). In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH groups from the polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required for the synthesis of the polyester phthalic acid, and the solvent may be directly left to form a liquid or gel-like photosensitive composition in consideration of workability or the like, or the solvent may be removed to take into consideration A solid composition such as portability. Further, the synthesis of the polyester phthalic acid may optionally contain one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material, and preferably contains a monohydroxy compound. Further, the synthesis of the polyester proline may be carried out as a raw material, if necessary, in addition to the object of the present invention. Examples of such other raw materials include monoamine-containing amines.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining polyester proline. Specific examples of preferred tetracarboxylic dianhydrides include: 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid Dihydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3, 3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Dihydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[double ( 3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, ethylene glycol bis(hydrogen trimellitate) (trade name; TMEG- 100, New Japan Physicochemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride and 3,3',4,4'-diphenyl which impart good transparency to the cured film are more preferable. Ethyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, and TMEG- 100, particularly preferably 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride and 1,2,3, 4-butane tetracarboxylic dianhydride.

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining a polyester proline. Specific examples of preferred diamines include 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylguanidine, and bis. [4-(4-Aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[3-(4-aminophenoxy)phenyl ][,(4-(4-Aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]anthracene, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl]anthracene, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. More than one of these diamines can be used.

Among these diamines, 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene which impart good transparency to the cured film are more preferable, and 3 is particularly preferable. 3'-Diaminodiphenylphosphonium.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as the material for obtaining the polyester phthalic acid. Specific examples of preferred polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and tripropylene glycol. Tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentane Glycol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6 - hexanetriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6 -octanediol, 1,2,8-octanetriol, 1,2-decanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1 , 10-decanediol, 1,2,10-nonanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, Tris(2-hydroxyethyl) isocyanate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)fluorene), double Phenol F (bis(4-hydroxyphenyl)methane), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxybicyclo Group, diethanolamine, and triethanolamine. One or more of these polyvalent hydroxy compounds may be used.

Among these polyvalent hydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7 having good solubility in a reaction solvent are more preferable. - heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl, and isocyanuric acid tris(2-hydroxyethyl) The esters are particularly preferably 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol.

1-1-4. Monohydroxy compound In the present invention, a monohydroxy compound can be used as the material for obtaining the polyester proline. By using a monohydroxy compound, the storage stability of the photosensitive composition can be improved. Specific examples of preferred monohydroxy compounds include benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyl oxetane and dimethylbenzyl methanol (dimethyl Benzyl carbinol). One or more of these monohydroxy compounds may be used.

Among these monohydroxy compounds, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are more preferable. Consider compatibility in the case where a polyester phthalic acid formed by using these monohydroxy compounds is mixed with an epoxy group-containing polymer, an epoxy compound, and an epoxy hardener, or a photosensitive composition in color filter For the coating property on the light sheet, it is particularly preferable to use benzyl alcohol as the monohydroxy compound.

The reaction is carried out by containing 0 to 300 parts by weight of a monohydroxy compound, based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 weight part - 200 weight part.

1-1-5. Styrene-maleic anhydride copolymer Further, the polyester phthalic acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the raw material. By carrying out as described above, the transparency of the cured film can be improved, which is preferable. An example of the compound having three or more acid anhydride groups is exemplified by a styrene-maleic anhydride copolymer. The molar ratio of styrene/maleic anhydride is from 0.5 to 4, preferably from 1 to 3, with respect to the ratio of each component constituting the styrene-maleic anhydride copolymer. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names; Chuan crude oil chemical company). Among these commercially available products, SMA1000P which is excellent in heat resistance and alkali resistance of the cured film is particularly preferable.

The styrene-maleic anhydride copolymer is preferably contained in an amount of from 0 to 500 parts by weight based on 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. It is more preferably 10 parts by weight to 300 parts by weight.

1-1-6. The monoamine-containing monoamine may be used as a raw material in the synthesis of the polyester phthalic acid, and may contain other raw materials other than the above, as needed, without departing from the object of the present invention. Examples of the raw material include a monoamine containing hydrazine.

Specific examples of the preferred fluorene-containing monoamine used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldi Methoxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethyl Oxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyldiethoxydecane And m-aminophenyltrimethoxydecane, and m-aminophenylmethyldiethoxydecane. One or more of these monoamine-containing monoamines can be used.

Among these monoamine-containing monoamines, 3-aminopropyltriethoxydecane and p-aminophenyltrimethoxydecane which improve the acid resistance of the cured film are more preferable from the viewpoints of acid resistance and compatibility. Particularly preferred is 3-aminopropyltriethoxydecane.

It is preferable to contain 0 to 300 parts by weight of a fluorene-containing monoamine with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 weight part - 200 weight part.

1-1-7. A solvent used in the synthesis reaction of the polyester valine acid, and a specific example of the solvent used in the synthesis reaction for obtaining the polyester glutamic acid: diethylene glycol dimethyl ether, Ethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Methyl ester, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable.

1-1-8. Method for synthesizing polyester phthalic acid The method for synthesizing polyester glutamic acid used in the present invention is to make tetracarboxylic dianhydride X-mole, diamine Y-mole in the solvent. And a polyhydroxy compound Z molar reaction. In this case, X, Y, and Z are preferably set to a ratio at which the relationship between the following formulas (1) and (2) is established between these X, Y, and Z. If it is this range, since the solubility of a polyester valine acid in a solvent is high, the coating property of a composition improves, and as a result, the cured film which is excellent in flatness can be obtained. 0.2≦Z/Y≦8.0 ·······(1)0.2≦(Y+Z)/X≦5.0 · (2) In the formula (1), 0.7≦Z/Y≦7.0 is preferable. More preferably, 1.0 ≦ Z / Y ≦ 5.0. Further, in the formula (2), 0.5 ≦ (Y + Z) / X ≦ 4.0 is preferable, and 0.6 ≦ (Y + Z) / X ≦ 2.0 is more preferable.

It is considered that the polyester phthalic acid used in the present invention is excessively formed at the end than the molecule having an amine group or a hydroxyl group at the terminal under the reaction conditions, in the case where X is excessively used with respect to Y+Z. A molecule having an acid anhydride group (-CO-O-CO-). When the reaction is carried out in the constitution of such a monomer, the terminal is subjected to esterification in order to react with an acid anhydride group at the terminal of the molecule, and the above-mentioned monohydroxy compound may be added as needed. The polyester proline obtained by the reaction by adding a monohydroxy compound can improve compatibility with an epoxy compound and an epoxy hardener, and can improve the coatability of the photosensitive composition of the present invention containing these compounds.

Further, when the reaction is carried out in the configuration of the monomer, a fluorene-containing monoamine may be added in order to introduce a decyl group at the terminal end to react with an acid anhydride group at the molecular terminal. When the photosensitive composition of the present invention containing polyester phthalic acid (which is obtained by adding a hydrazine monoamine-containing reaction) is used, the acid resistance of the obtained cured film can be improved. Further, when the reaction is carried out in the configuration of the monomer, a reaction between the monohydroxy compound and the monoamine-containing monoamine may be carried out.

When 100 parts by weight or more of the reaction solvent is used per 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at a temperature of from 40 ° C to 200 ° C for from 0.2 hours to 20 hours.

The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods may be used: a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound are simultaneously added to a reaction solvent; and after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, tetracarboxylic dianhydride is added. After the tetracarboxylic dianhydride and the polyvalent hydroxy compound are previously reacted, a diamine is added to the reaction product; or the tetracarboxylic dianhydride and the diamine are previously reacted, and a polyvalent hydroxy compound or the like is added to the reaction product.

In the case of reacting the ruthenium-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the monoamine-containing amine is added at 10 ° C. The reaction is carried out at -40 ° C for 0.1 hour to 6 hours. Moreover, a monohydroxy compound can be added at any point in the reaction.

The polyester phthalic acid synthesized as described above contains the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and the terminal is derived from tetracarboxylic dianhydride as a raw material, and An acid anhydride group, an amine group or a hydroxyl group of an amine or a polyvalent hydroxy compound, or an additive other than these compounds constitutes a terminal. By including such a structure, hardenability becomes favorable.

The weight average molecular weight of the obtained polyester phthalic acid is preferably from 1,000 to 200,000, more preferably from 3,000 to 50,000. If it is in these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained 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, Agilent Technologies, Inc., polystyrene calibration kit PL2010-0102), column using PLgel MIXED-D (Agilent Technologies, Inc.) can be measured using Tetrahydrofuran (THF) as the mobile phase. Further, the weight average molecular weight of the commercially available product in the present specification is a catalogue value.

1-2. Compound having a polymerizable double bond 1-2-1. Compound having two or more polymerizable double bonds per molecule The compound having a polymerizable double bond used in the present invention is not particularly limited. It is preferably a compound having two or more polymerizable double bonds per molecule. When the compound having a polymerizable double bond is 50 parts by weight to 300 parts by weight based on 100 parts by weight of the polyester phthalic acid, the residual film ratio after development is improved, which is preferable.

The compound having two or more polymerizable double bonds per molecule contained in the photosensitive composition of the present invention may, for example, be ethylene glycol di(meth)acrylate or diethylene glycol di(methyl). Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol di(a) Acrylate, epichlorohydrin-modified diethylene glycol di(meth)acrylate, epichlorohydrin-modified triethylene glycol di(meth)acrylate, epichlorohydrin-modified tetraethylene glycol di( Methyl) acrylate, epichlorohydrin modified polyethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, dipropylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate Ester, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin-modified propylene glycol di(meth)acrylate, epichlorohydrin-modified dipropylene glycol di(meth)acrylate , epichlorohydrin-modified tripropylene glycol di(meth)acrylate, epichlorohydrin-modified tetrapropylene glycol di(meth)acrylate, epichlorohydrin-modified polypropylene glycol II Acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tris(A) Acrylate, epichlorohydrin-modified trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol (meth)acrylate, glycerol Acrylate, tris(meth)acrylate, epichlorohydrin-modified glycerol tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, epichlorohydrin modification 1, 6-hexanediol di(meth)acrylate, methoxycyclohexyl (meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(a) Acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di(meth) acrylate, diglycerin tetra(meth) acrylate, diglycerin oxirane modified acrylate, pentaerythritol III Methyl) acrylate, pentaerythritol tetra(meth) acrylate, stearic acid modified pentaerythritol di(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipenta Tetraol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Ester-modified dipentaerythritol hexa(meth) acrylate, polyacid-modified (meth) acrylate oligomer, allylic cyclohexyl di(meth) acrylate, bis[(meth) propylene decyloxy Neopentyl glycol] adipate, bisphenol A di(meth) acrylate, ethylene oxide modified bisphenol A di(meth) acrylate, bisphenol F di(meth) acrylate, ring Oxyethane modified bisphenol F di(meth)acrylate, bisphenol S di(meth)acrylate, ethylene oxide modified bisphenol S di(meth)acrylate, 1,4-butane Alcohol di(meth)acrylate, 1,3-butanediol (meth)acrylate, dicyclopentyl diacrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, poly Ester pentaacrylate, polyester hexaacrylate, ethylene oxide modified di(meth)acrylate, ethylene oxide modified tris(meth)acrylate, ethylene oxide modified phosphoric acid Methacrylate Ethylene oxide modified tris(meth)acrylate, epichlorohydrin modified di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, triglycerin II Methyl) acrylate, neopentyl glycol modified trimethylolpropane di(meth) acrylate, iso-cyanuric acid ethylene oxide modified diacrylate, iso-cyanuric acid ethylene oxide Triacrylate/caprolactone modified tris[(methyl)acryloxyethyl)isotrisocyanate, (meth)acrylated isomeric cyanurate, phenyl glycidyl ether acrylate /hexamethylene diisocyanate / urethane prepolymer, phenyl glycidyl ether acrylate / toluene diisocyanate / urethane prepolymer, pentaerythritol triacrylate / hexamethylene diisocyanate / Urethane prepolymer, pentaerythritol triacrylate/toluene diisocyanate/urethane prepolymer, pentaerythritol triacrylate/isophorone diisocyanate/urethane prepolymer, dipentaerythritol Pentaacrylate/hexamethylene diisocyanate/urethane prepolymer, non-yellowing type oligomeric urethane acrylate An acid ester, a carboxylic acid-containing urethane acrylate oligomer, an epoxy acrylate oligomer, or the like.

The compound having two or more polymerizable double bonds per molecule may be used singly or in combination of two or more.

From the viewpoint of heat resistance and chemical resistance of the cured film, it is preferable to use trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol, and a compound having two or more polymerizable double bonds per molecule. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid-modified (meth)acrylic acid oligomer, iso-cyanuric acid-modified diacrylate, iso-cyanuric acid ring Oxyethane modified triacrylate, epoxy acrylate oligomer or a mixture of these.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid modified (meth)acrylic acid oligomer, iso-cyanuric acid ring As the oxyethylene modified diacrylate, the isomeric cyanuric acid ethylene oxide modified triacrylate, the epoxy acrylate oligomer, or a mixture of these, a commercially available product such as the following can be used. A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; East Asia Synthetic Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronix M-306 (65% by weight to 70% by weight), and Aronix M-305 (55% by weight to 63% by weight). %), Aronix M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight), and Aronix M- 450 (less than 10% by weight, hereinafter abbreviated as "M-450") (all are trade names; East Asia Synthetic Co., Ltd., the content rate in parentheses is a catalogue value of the content rate of pentaerythritol triacrylate in the mixture). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% by weight to 60% by weight) and Aronix M-400 (40% by weight - 50% by weight), Aronix M-402 (30% to 40% by weight, hereinafter abbreviated as "M-402"), and Aronix M-404 (30% to 40% by weight) ), Aronix M-406 (25% to 35% by weight), and Aronix M-405 (10% to 20% by weight) (all are trade names; East Asia Synthetic Co., Ltd.) The content in the company and the brackets is a list of the contents of the content of dipentaerythritol pentaacrylate in the mixture). Specific examples of the polyacid-modified (meth)acrylic oligomer are Aronix M-510 and Aronix M-520 (both trade names; East Asia Synthetic Co., Ltd.). A specific example of the isomeric cyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name; East Asia Synthetic Co., Ltd.). A specific example of a mixture of isomeric cyanuric acid ethylene oxide modified diacrylate and isomeric cyanuric acid ethylene oxide modified triacrylate is Aronix M-313 (30% by weight to 40%) (% by weight) and Aronix M-315 (3% by weight to 13% by weight, hereinafter abbreviated as "M-315") (both trade names; East Asia Synthetic Co., Ltd., the content in parentheses is a mixture) The catalogue of the content of the iso-cyanuric acid-modified diacrylate in the catalogue). A specific example of the epoxy acrylate oligomer is TEA-100 (trade name; KSM Co., Ltd.).

1-2-2. A photosensitive compound having a polymerizable double bond in each molecule and having at least one functional group selected from -OH and -COOH in each molecule from the viewpoint of resolving The sexual composition may further contain a compound having one polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH in each molecule. If the compound having one polymerizable double bond in each molecule and having at least one functional group selected from -OH and -COOH in each molecule is 1 part by weight based on 100 parts by weight of the polyester phthalic acid - When 50 parts by weight, the analytical property is improved and it is preferable.

Such a compound having one polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH in each molecule may, for example, be (meth)acrylic acid or (meth)acrylic acid. Hydroxyethyl ester, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(methyl) succinate Propylene methoxyethyl ester, hexahydrophthalic acid 2-(methyl) propylene methoxyethyl ester, phthalic acid-2-(methyl) propylene methoxyethyl ester, phthalic acid 2- (Meth)acryloyloxyethyl-2-hydroxyethyl ester, (meth)acrylic acid-4-hydroxyphenyl ester, p-hydroxy(meth)acrylic acid anilide, (meth)acrylic acid-4-hydroxybutyl Ester, 1,4-cyclohexanedimethanol mono(meth)acrylate, glycerol mono(meth)acrylate,-3-(2-hydroxyphenyl)acrylate, and (meth)acrylic acid-β- Carboxyethyl ester.

Among these compounds, the analytical property of 4-hydroxyphenyl (meth)acrylate and phenylamine (meth)acrylate is preferred, and it is preferable.

1-3. Photopolymerization initiator The photopolymerization initiator contained in the photosensitive composition of the present invention is not particularly limited as long as it can initiate polymerization of the following composition, and the composition contains polyester. A proline acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent, and a molecular weight modifier.

The photopolymerization initiator contained in the photosensitive composition of the present invention may, for example, be benzophenone, micbutone, 4,4'-bis(diethylamino)benzophenone or xanthene. Ketone, thioxanthone, isopropyl oxa ketone, 2,4-diethyl thia fluorenone, 2-ethyl hydrazine, acetophenone, 2-hydroxy-2-methylpropiophenone, 2 -hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane 1-ketone (for example, trade name; IRGACURE 907, BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholino) Phenyl)-butanone-1 (for example, trade name; IRGACURE 369, BASF Japan Co., Ltd.), 4-dimethylaminobenzoic acid ethyl ester, 4-dimethyl Isoamyl benzoate, 4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(tert-butylperoxycarbonyl)benzophenone, 1, 2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzhydrylhydrazine) (for example, trade name; IRGACURE OXE-01, BASF Japan) BASF Japan), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9-oxazol-3-yl]-, 1-(O-acetamidine) (e.g., trade name; IRGACURE OXE-02, BASF Japan Co., Ltd.), OXE-03 (for example, trade name; BASF Japan Co., Ltd.), 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-ethylindenyl) (for example, trade name; Eddie ADEKA ARKLS NCI-930, ADEKA Co., Ltd., ADEKA ARKLS NCI-831 (trade name; ADEKA shares limited) Company), ADEKA OPTOMER N-1919 (trade name; ADEKA), 2,4,6-trimethylbenzhydryldiphenylphosphine oxide , 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4 , 6-double ( Chloromethyl)-s-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-A Oxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-all Triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl)]-2,6-di(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl) -5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(pair two Methylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-sulfobenzothiazole, 3,3'-carbonyl bis(7-diethyl) Amino-based coumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorobenzene -4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)- 4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-four Phenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked Imidazole, 3-(2-methyl-2-dimethylaminopropionyl)carbazole, 3,6-bis(2-methyl-2-morpholinopropanyl)-9-positive Alkyl hydrazine Oxazole, 1-hydroxycyclohexyl phenyl ketone, and bis(h ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl) )-phenyl) titanium or the like.

The photopolymerization initiator may be used singly or in combination of two or more. From the viewpoint of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, the photopolymerization initiator is preferably an α-aminophenylalkylketone-based, mercaptophosphine oxide-based or oxime-based photopolymerization. Starting agent. Further, in the present specification, the film is referred to as a "coating film" which is prepared by drying (prebaking) a film of a photosensitive composition formed by spin coating, printing, or the like on a substrate. obtain. The coating film is subjected to a subsequent exposure-development-washing-drying step and the like, and is subjected to a conventional calcination (post-baking) to form a cured film. In the present specification, the film in the step from the preliminary heating to the drying is referred to as a "coating film", and is expressed, for example, by the expression "coating film at the time of exposure" or "coating film after development". At what stage of the film step the coating film.

From the viewpoint of the sensitivity of the coating film and the transparency of the cured film, among the photopolymerization initiators, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2 is more preferable. -(O-benzhydrylhydrazine) or 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-acetamidine) The base layer is 20% by weight or more based on the total weight of the photopolymerization initiator. Moreover, it is more preferable if it is 50 weight% or more. The photopolymerization initiator may also contain only 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine) or 1,2-propanedione. 1-[4-[4-(2-Hydroxyethoxy)phenylthio]phenyl]-2-(O-ethylindenyl).

1-4. Molecular weight adjuster A molecular weight modifier is used for the photosensitive composition of the present invention in order to suppress a high molecular weight due to polymerization and to exhibit excellent resolution. Examples of the molecular weight modifier include mercaptans, xanthates, anthraquinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthoquinone, and 2,5-di-tert-butylhydroquinone. , hydroquinone, methylhydroquinone, tert-butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, anthracene, n-hexyl mercaptan, n-octyl Thiol, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid, dimethylxanthogen thioether, diisopropyl xanthogen disulfide, 2,4-di Phenyl-4-methyl-1-pentene and the like.

The molecular weight modifier may be used singly or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred from the viewpoint of exhibiting excellent analytical properties. Further, it is also preferable from the viewpoint of suppressing the cured film after the analysis and the pleats in the vicinity of the substrate. The hem is shown in the vicinity of the substrate, and the non-analytical portion protrudes to the analysis portion.

Among the molecular weight modifiers, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferable from the viewpoint of resolution. In addition, it is preferable that the content of the photopolymerization initiator is more than 5.0 times and less than 30 times the content of the molecular weight modifier, and it is more preferable to start with photopolymerization. The molecular weight modifier is contained in such a manner that the content of the agent is more than 5.1 times and not more than 20 times the content of the molecular weight modifier. Furthermore, it is more preferable to contain a molecular weight modifier in such a manner that the content of the photopolymerization initiator is more than 5.2 times and 10 times or less the content of the molecular weight modifier.

1-5. Epoxy Compound The epoxy compound used in the present invention contains two to ten epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding an epoxy compound to the photosensitive composition of the present invention, the heat resistance of the cured film can be improved. When the epoxy compound is 20 parts by weight to 150 parts by weight based on 100 parts by weight of the polyester phthalic acid, the flatness is improved, which is preferable.

Preferable examples of the epoxy compound include 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester (for example, trade name; Celloxide 2021P, Daicel) (Daicel) Co., Ltd.), 1-methyl-4-(2-methyloxacyclopropyl)-7-oxabicyclo[4.1.0]heptane (for example, trade name; Cerroside ( Celloxide) 3000, Daicel Co., Ltd., 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2 ,3-glycidoxy)phenyl]ethyl]phenyl]propane with 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1 a mixture of [4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl Phenyl]propane (for example, trade name; TECHMORE VG3101L, Printec), 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether ( For example, trade name; JER 1032H60, Mitsubishi Chemical Corporation), 1,3-bis(oxopropylmethyl)-5-(2-propenyl)-1,3,5-triazine-2 , 4,6(1H,3H,5H)-trione, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxopropyl) A cyclohexane adduct (for example, trade name; EHPE-3150, Daicel Co., Ltd.) or the like.

1-6. Epoxy Curing Agent In the photosensitive composition of the present invention, an epoxy curing agent is used in order to improve flatness and chemical resistance. The epoxy curing agent includes an acid anhydride-based curing agent, an amine-based curing agent, a phenol-based curing agent, an imidazole-based curing agent, a catalyst-type curing agent, and a sensible salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt or a phosphonium salt. The acid generator-based curing agent or the imidazole-based curing agent is preferred from the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides (for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrogen). An aromatic polycarboxylic acid anhydride (for example, phthalic anhydride or trimellitic anhydride). Among these acid anhydride-based curing agents, trimellitic anhydride and hexahydrotrimellitic anhydride which can improve the heat resistance of the cured film without impairing the solubility of the photosensitive composition in a solvent are particularly preferable.

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

1-7. The ratio of the polyester phthalic acid, the compound having a polymerizable double bond, the photopolymerization initiator, the epoxy compound, the epoxy curing agent, and the molecular weight modifier is in the photosensitive composition of the present invention, relative to The ratio of the compound having a polymerizable double bond to 100 parts by weight of the polyester phthalic acid is 20 parts by weight to 300 parts by weight. When the ratio of the compound having a polymerizable double bond is in this range, the balance between heat resistance, flatness, chemical resistance, and residual film ratio after development is good. Further, the compound having a polymerizable double bond is more preferably in the range of 100 parts by weight to 300 parts by weight.

The ratio of the photopolymerization initiator is from 2 parts by weight to 60 parts by weight based on 100 parts by weight of the polyester phthalic acid. From the viewpoint of the sensitivity of the coating film at the time of exposure, it is preferable that the ratio of the photopolymerization initiator is in the above range. Further, from the viewpoint of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, in the photopolymerization initiator, if 1,2-octanedione-1-[4-(phenylthio)phenyl] -2-(O-benzylidene hydrazine) or 1,2-propanedione-1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O- The acetonitrile group is more preferably 20% by weight or more based on the total weight of the photopolymerization initiator. Moreover, it is more preferable if it is 50 weight% or more.

In the photosensitive composition of the present invention, the ratio of the epoxy compound is from 20 parts by weight to 200 parts by weight based on 100 parts by weight of the polyester phthalic acid. When the ratio of the epoxy compound is in this range, the balance between heat resistance and flatness is good. It is more preferable if the epoxy compound is in the range of 20 parts by weight to 150 parts by weight.

The ratio of the epoxy curing agent to the epoxy compound is from 0.1 part by weight to 60 parts by weight based on 100 parts by weight of the epoxy compound and the epoxy curing agent. For example, in the case where the epoxy curing agent is an acid anhydride-based curing agent, the amount of the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is preferably 0.1 times equivalent to the epoxy group. Add in 1.5 equivalents. At this time, the carboxylic anhydride group was calculated at a divalent value. When the carboxylic anhydride group or the carboxyl group is added in an amount of from 0.15 to 0.8 equivalents, the chemical resistance is further improved, and thus it is more preferable.

1-8. Other components Various additives may be added to the photosensitive composition of the present invention to improve coating uniformity and adhesion. The additives may mainly be solvents, anionic, cationic, nonionic, fluorine or lanthanide leveling agents/surfactants, coupling agents such as decane coupling agents, hindered phenolic, hindered amines, phosphorus, and sulfur. An antioxidant such as a compound.

1-8-1. Solvent A solvent may be added to the photosensitive composition of the present invention. The solvent to be added arbitrarily in the photosensitive composition of the present invention is preferably a solvent which can dissolve a polyester phthalic acid, a compound having a polymerizable double bond, an epoxy compound, or an epoxy curing agent. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxylate. Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , propyl pyruvate, methyl acetate methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether Ester, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

1-8-2. Surfactant In the photosensitive composition of the present invention, a surfactant may be added to improve coating uniformity. 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, Diss Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Diss Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all are trade names; Japan BYK Chemical (BYK Chemie Japan) Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Shafu Surflon SC-101, Surflon KH-40, Surflon S611 (all are trade names; AGC clear AGC Seimi Chemical Co., Ltd., Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, and Fortune (Fatgent) Ftergent) 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (both trade names; Neos Co., Ltd.), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (both trade names; Mitsubishi Material Co., Ltd., Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Meijiafa ( Megafac) F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553 , Megafac F-554, Megafac F-555, Mei Jiafa (M Egafac) F-556, Megafac F-558, Megafac F-559, Megafac R-30, Megafac R-94, Megafac RS-75 , Megafac RS-72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names; Di Ai Sheng (DIC) Co., Ltd.), Di Gao (TEGO Twin) 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, Digog TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (both trade names, Evonik-Degussa Japan Co., Ltd.) Fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl) Polyoxyethylene ether), fluoroalkyl trimethyl ammonium salt, fluoroalkyl amine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, poly Oxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oil Acid esters, polyoxyethylene stearates, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan Fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl Ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferred to use at least one selected from these compounds.

Among these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Meijiafa (Megafac) RS-72-k, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, At least one of the fluoroalkyl sulfonate, the fluoroalkyltrimethylammonium salt, and the fluoroalkylaminosulfonate is preferred because the coating uniformity of the photosensitive composition is high.

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

1-8-3. 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 decane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples thereof include 3-glycidoxypropyl dimethyl ethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, and 3-glycidoxy propyl trimethoxy decane. (for example, trade name; Sila-Ace S510, JNC), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (for example, trade name) ; Sila-Ace S530, JNC (JNC), 3-mercaptopropyltrimethoxydecane (for example, trade name; Sila-Ace S810, Jie Enzhi) Copolymer of (JNC) Co., Ltd., 3-glycidoxypropyltrimethoxydecane (for example, trade name; CoatOSil MP200, Momentive Performance Materials Co., Ltd.) An arsenic-based coupling agent, an aluminum-based coupling agent such as acetaloxydiisopropylaluminate or a titanate-based coupling agent such as tetraisopropylbis(dioctylphosphite) titanate.

Among these coupling agents, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving the 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, and the adhesion between the formed cured film and the substrate can be improved, which is preferable.

1-8-4. Antioxidant The photosensitive composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing of the cured film when exposed to a high temperature.

An antioxidant such as a hindered phenol type, a hindered amine type, a phosphorus type or a sulfur type compound may be added to the photosensitive composition of the present invention. Among them, a hindered phenol type is preferred from the viewpoint of weather resistance. Specific examples can be cited: Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Easy Ginos (Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Yi Gannos (Irganox) 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Yi Gan Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yi Zhanno Irganox 565DD, Irganox 295 (both trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, Eddie Costabo (ADK STAB) AO-30, ADIK STAB AO-50, ADK STAB AO-60,迪科斯塔波 (ADK STAB) AO-70, Addison Costa wave (ADK STAB) AO-80 (both trade names; manufactured by ADEKA (ADEKA) Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferable.

To the total amount of the photosensitive composition, 0.1 part by weight to 10 parts by weight of an antioxidant is added and used.

1-8-5. Other additives The photosensitive composition of the present invention may further contain a polymer (hereinafter sometimes referred to as "radical copolymerized polymer") which is obtained by the following formula (6) The radically polymerizable compound (a1), the radically polymerizable compound (a2) having an alkoxyalkyl group, and the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group Free radical copolymerization is carried out.

(R ⁸ is hydrogen or methyl, R ⁹ to R ¹² are alkyl groups having 1 to 5 carbon atoms, R ¹³ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer)

1-8-5-1. Radical Polymerizable Compound (a1) The radically polymerizable compound (a1) represented by the formula (6) functions as a surfactant, and therefore (a1) is used as a raw material. Further, the radical copolymerization polymer acts as a surfactant, and the flatness, the adhesion to the base substrate, and the coatability can be improved without adding a surfactant. By adding the radically polymerizable compound (a1), the radical copolymer polymer becomes easy to surface on the surface of the film.

In the present invention, in the radically polymerizable compound (a1) represented by the formula (6), R ⁸ is preferably hydrogen or a methyl group, R ⁹ to R ¹² are a methyl group, and R ¹³ is a carbon number of 1 to 10. An alkyl group, m is an integer of from 1 to 5, and n is a compound of an integer of from 1 to 150. More preferably, R ⁸ is a methyl group, R ⁹ to R ¹² are a methyl group, R ¹³ is a butyl group, m is 3, and n is an integer of 1 to 150, and more preferably n is an integer of 30 to 70. The compound is particularly preferably a compound in which n is an integer of from 50 to 70. The radically polymerizable compound (a1) represented by the formula (6) preferably has a weight average molecular weight of 500 to 8,000.

The radically polymerizable compound (a1) can be produced by a known method. Moreover, a commercial item can also be used. For example, FM-0711, FM-0721, and FM-0725 (all of which are trade names; J&J (JNC) Co., Ltd.) and the like can be cited.

1-8-5-2. A radically polymerizable compound (a2) having an alkoxyalkyl group. In the present invention, a radically polymerizable compound (a2) having an alkoxyalkyl group is used to obtain the freedom. A raw material for a base copolymer. A preferred radically polymerizable compound (a2) is selected from the group consisting of 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3- (Meth) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy One or more of the group consisting of decane and p-styryltrimethoxydecane. Among these radically polymerizable compounds, 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropyltriethoxydecane are preferred because of their good flatness. By using (a2), transparency, chemical resistance, and the like are improved. Further, the adhesion to the substrate is improved by the decane coupling effect.

1-8-5-3. A radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group. In the present invention, at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group is free. The base polymerizable compound (a3) acts to obtain a raw material of the radical copolymer polymer. The preferred radically polymerizable compound (a3) is selected from the group consisting of glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid, and 4-hydroxyphenylvinyl More than one of the groups consisting of ketones. (a3) It functions as a crosslinking agent of a polymer, and contributes to improvement of heat resistance, chemical resistance, etc..

1-8-5-4. Method for producing a radical copolymerized polymer The radical polymerizable polymer is a radical polymerizable compound (a1) represented by the formula (6) and having alkoxyalkylene group. The compound (a2) and the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group are obtained by radical copolymerization. The method for producing the radical copolymerized polymer is not particularly limited, and the radical polymerizable compound can be heated in the presence of a radical initiator to produce a radical copolymerized polymer. As the radical initiator, an organic peroxide, an azo compound or the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 ° C to 150 ° C. The reaction time is also not particularly limited, but is usually in the range of 1 hour to 48 hours. Further, the reaction can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent used in the radical copolymerization reaction is preferably a solvent which dissolves the produced polymer. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxylate. Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , propyl pyruvate, methyl acetate methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether Ester, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

In the radical copolymerized polymer used in the present invention, the solvent used in the polymerization may be directly left to form a radical copolymerized polymer solution in consideration of workability or the like, or the solvent may be removed for consideration. A solid-state radical copolymerized polymer such as portability.

When the weight average molecular weight determined by gel permeation chromatography (GPC) analysis using a polystyrene standard is in the range of 1,000 to 50,000, the film-forming property is good, and it is preferable. Further, when the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is good, and it is more preferable. Further, when the weight average molecular weight is in the range of 2,500 to 15,000, the cured film is excellent in flatness and chemical resistance, and is particularly preferable.

0.1 to 20 parts by weight of other additives are added to the total amount of the photosensitive composition and used.

1-9. Storage of Photosensitive Composition When the photosensitive composition of the present invention is stored in the range of -30 ° C to 25 ° C, the stability with time of the composition is improved, 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 obtained from photosensitive composition The photosensitive composition of the present invention can be obtained by using polyester phthalic acid, a compound having a polymerizable double bond, an epoxy compound, an epoxy hardener, and a molecular weight. The adjusting agent is mixed, and depending on the target characteristics, a solvent, a coupling agent, a surfactant, and other additives are further selectively added as needed, and these compounds are uniformly mixed and dissolved.

When the photosensitive composition prepared as described above (in the case of a solid state without a solvent, dissolved in a solvent) is applied onto the surface of the substrate, the solvent is removed by, for example, heating or the like, and a coating film can be formed. . A conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexographic printing method, a spray method, or a slit coating method can be used to apply the photosensitive composition to the surface of the substrate. Next, the coating film is heated (prebaked) by a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio, and are usually from 70 ° C to 150 ° C, from 5 minutes to 15 minutes in the case of an oven, and from 1 minute to 5 minutes in the case of using a hot plate.

Thereafter, the mask is irradiated with ultraviolet rays by a mask that is separated from the desired pattern shape. Suitably, the amount of ultraviolet radiation is from 5 mJ/cm ² to 1000 mJ/cm ² in terms of i-rays. The photosensitive composition irradiated with ultraviolet rays is polymerized by a compound having a polymerizable double bond to form a three-dimensional crosslinked body, and is insolubilized in an alkaline developing solution.

Next, the coating film is immersed in an alkaline developing solution by spray development, spray development, liquid coating development, immersion development, or the like, and an unnecessary portion is dissolved and removed. Specific examples of the alkaline developing solution 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 or tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, a surfactant, or the like may be added to the alkaline developer to be used.

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

When the cured film obtained as described above is heated, 1) the polyamic acid moiety of the polyester phthalic acid is dehydrated and cyclized to form a quinone bond, and 2) the carboxylic acid and the ring containing the polyester phthalic acid Since the polymer of an oxy group reacts with a high molecular weight, it is very strong, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state imaging element. Further, the cured film of the present invention is effective as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Further, the cured film of the present invention is effective even as a protective film for an LED illuminator. [Examples]

Next, the present invention will be specifically described by way of Synthesis Examples, Reference Examples, Examples, and Comparative Examples, but the present invention is not limited by these examples. First, a polyester proline solution containing a reaction product of tetracarboxylic dianhydride, diamine, polyvalent hydroxy compound or the like is synthesized as follows (Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, Synthesis Example 4, Synthesis Example) 5. Synthesis Example 6 and Synthesis Example 7).

[Synthesis Example 1] Synthesis of polyester phthalic acid solution (A1) In a four-necked flask equipped with a stirrer, methyl 3-methoxypropionate which was subjected to dehydration purification was charged in the following weight (hereinafter abbreviated as " MMP"), 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol, benzyl alcohol, under a dry nitrogen stream, 130 ° C Stir for 3 hours. MMP 446.96 g ODPA 183.20 g 1,4-butanediol 31.93 g benzyl alcohol 25.54 g

Thereafter, the reaction liquid was cooled to 25 ° C, and 3,3'-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") and MMP were added in the following weight, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours. The mixture was stirred at 115 ° C for 1 hour. DDS 29.33 g MMP 183.04 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A1) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 4,200.

[Synthesis Example 2] Synthesis of polyester glutamic acid solution (A2) In a four-necked flask equipped with a stirrer, MMP, ODPA, 2,2-bis (4- Hydroxycyclohexyl)propane and benzyl alcohol were stirred at 130 ° C for 3 hours under a stream of dry nitrogen. MMP 445.93 g ODPA 153.02 g 2,2-bis(4-hydroxycyclohexyl)propane 71.15 g benzyl alcohol 21.34 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 24.50 g MMP 174.07 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A2) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A2) was 4,000.

[Synthesis Example 3] Synthesis of Polyester Proline Solution (A3) In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate which was subjected to dehydration purification was sequentially added in the following weight (hereinafter abbreviated as " PGMEA"), 1,2,3,4-butanetetracarboxylic dianhydride (hereinafter abbreviated as "BT-100"), 2,2-bis(4-hydroxycyclohexyl)propane, benzyl alcohol, in dry nitrogen The mixture was stirred at 130 ° C for 3 hours under running. PGMEA 444.22 g BT-100 122.90 g 2,2-bis(4-hydroxycyclohexyl)propane 89.47 g benzyl alcohol 26.83 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 30.80 g MMP 185.78 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A3) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A3) was 3,800.

[Synthesis Example 4] Synthesis of polyester glutamic acid solution (A4) In a four-necked flask equipped with a stirrer, MMP, ODPA, 2,2-bis (4- Hydroxycyclohexyl)propane was stirred at 130 ° C for 3 hours under a stream of dry nitrogen. MMP 483.84 g ODPA 187.78 g 2,2-bis(4-hydroxycyclohexyl)propane 72.75 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 9.47 g MMP 146.16 g [Z/Y=7.9, (Y+Z)/X=0.6]

The solution was cooled to room temperature to obtain a 30 wt% solution (A4) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A4) had a weight average molecular weight of 3,500.

[Synthesis Example 5] Synthesis of Polyester Amidinic Acid Solution (B1) PGMEA, BT-100, and SMA1000P (trade name; benzene) which were subjected to dehydration purification were sequentially placed in a four-necked flask equipped with a stirrer under the following weights. Ethylene-maleic anhydride copolymer, Chuan crude oil Co., Ltd.), 1,4-butanediol, and benzyl alcohol were stirred at 125 ° C for 3 hours under a stream of dry nitrogen. PGMEA 481.37 g BT-100 34.47 g SMA1000P 164.11 g 1,4-butanediol 10.45 g benzyl alcohol 50.17 g

Thereafter, the reaction liquid was cooled to 25° C., DDS and PGMEA were added in the following weight, stirred at 20° C. to 30° C. for 2 hours, and then stirred at 125° C. for 2 hours. DDS 10.80 g PGMEA 148.63 g [Z/Y=2.7, (Y+Z)/X=0.9]

The solution was cooled to room temperature to obtain a 30 wt% solution (B1) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B1) was 10,000.

[Synthesis Example 6] Synthesis of Polyester Amidinic Acid Solution (B2) PGMEA, BT-100, SMA1000P, and 1,4-100 were subjected to dehydration purification in a four-necked flask equipped with a stirrer in the following order. Butanediol and benzyl alcohol were stirred at 125 ° C for 3 hours under a stream of dry nitrogen. PGMEA 494.87 g BT-100 33.80 g SMA1000P 160.93 g 1,4-butanediol 10.25 g benzyl alcohol 61.49 g

Thereafter, the reaction liquid was cooled to 25° C., DDS and PGMEA were added in the following weight, stirred at 20° C. to 30° C. for 2 hours, and then stirred at 125° C. for 2 hours. DDS 3.53 g PGMEA 135.13 g [Z/Y=8.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (B2) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (B2) had a weight average molecular weight of 9,000.

[Synthesis Example 7] Synthesis of Polyester Amidinic Acid Solution (B3) In a four-necked flask equipped with a stirrer, PGMEA and diethylene glycol methyl ethyl ether which were subjected to dehydration purification were sequentially placed under the following weights ( Hereinafter, it is abbreviated as "EDM"), ODPA, SMA1000P, 1,4-butanediol, and benzyl alcohol, and the mixture was stirred at 120 ° C for 3 hours under a nitrogen stream. PGMEA 504.00 g EDM 96.32 g ODPA 47.7 g SMA1000P 144.97 g 1,4-butanediol 9.23 g benzyl alcohol 55.40 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 120 ° C for 2 hours. DDS 12.72 g EDM 29.68 g [Z/Y=2.0, (Y+Z)/X=1.0]

The solution was cooled to room temperature to obtain a 30 wt% solution (B3) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B3) was 21,000.

Next, the following copolymer was synthesized as a radical copolymerized polymer by radical polymerization of a radical polymerizable compound (a1) represented by the formula (6) and having an alkoxyalkyl group The radical compound (a2) and the radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group are obtained by radical copolymerization (Synthesis Example 8).

[Synthesis Example 8] Synthesis of a solution of a radical copolymerized polymer (D) In a four-necked flask equipped with a stirrer, dehydrated and purified EDM as a polymerization solvent was charged as a radically polymerizable compound ( FM-0721 of a1) (in the formula (6), R ⁸ to R ¹² are methyl groups, R ¹³ is butyl group, m=3, n=66, weight average molecular weight: 5,000, and JC has limited shares a 3-methylpropenyloxypropyltrimethoxydecane which is a radically polymerizable compound (a2) having an alkoxyalkylalkyl group, and has at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group. The glycidyl methacrylate of the radically polymerizable compound (a3) is further charged with 2,2'-azobis(2-methylpropionic acid) dimethyl ester as a polymerization initiator in the following weight (V- 601; trade name; Wako Pure Chemical Industries Co., Ltd.) was stirred at 90 ° C for 2 hours under a stream of dry nitrogen. EDM 40.00 g FM-0721 0.20 g glycidyl methacrylate 8.00 g 3-methylpropenyloxypropyltrimethoxydecane 11.80 g V-601 2.00 g

The solution was cooled to room temperature to obtain a 33.3 wt% solution of the radical copolymer polymer (D). A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained radical copolymer polymer (D) was 7,800.

[Example 1] A 1000 ml separable flask equipped with a stirring blade was purged with nitrogen, and 131.74 g of the polyester proline solution (A1) obtained in Synthesis Example 1 and 39.52 g were charged in the flask. M-520 as a compound having a polymerizable double bond, 6.59 g of NCI-930 as a photopolymerization initiator, 1.10 g of 2-hydroxy-1,4-naphthoquinone as a molecular weight modifier, and 52.69 g VG3101L of an epoxy compound, 6.59 g of trimellitic anhydride as an epoxy curing agent (hereinafter abbreviated as "TMA"), and 2.47 g of 3-glycidoxypropyltrimethoxydecane as an additive (for example, a commercial product) Name; Sila-Ace S510, JNC) and 1.48 g of ADK STAB AO-60 (trade name; ADEKA) Company), 187.71 g of dehydrated purified MMP and 69.98 g of EDM as a solvent were stirred at room temperature for 3 hr to be uniformly dissolved. Next, 0.13 g of Megafac F-556 (trade name; Di Ai Sheng (DIC) Co., Ltd.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered by a membrane filter (0.2 μm) to prepare photosensitivity. Composition.

The photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and prebaked on a hot plate at 100 ° C for 80 seconds. Next, in the air, a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) was used and exposure was performed. The exposure amount was measured by using an integrated light meter UIT-102 (trade name; oxtail (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; oxtail (USHIO) Co., Ltd.) to be 30 mJ/cm. ² . The coating film after exposure was subjected to liquid-coating development at 27 ° C for 40 seconds using a buffer solution of sodium carbonate x sodium hydrogencarbonate, and then the coating film was washed with pure water for 20 seconds, and then subjected to a hot plate at 100 ° C for 2 minutes. dry. Further, it was post-baked in an oven at 230 ° C for 30 minutes to obtain a glass substrate with a cured film having a film thickness of 1.5 μm.

The cured film obtained as described above was evaluated for the residual film ratio, heat resistance, transparency, resolution, and flatness after development.

[Method for Evaluating Residual Film Rate after Development] The film thickness before development and the film thickness after development were measured using a step, surface roughness, and fine shape measuring device (trade name; P-16, KLA TENCOR Co., Ltd.). Then, the residual film ratio after development (film thickness after development × 100 / film thickness before development) was calculated. The case where the residual film ratio after development was 80% or more was evaluated as ○, and the case where the residual film ratio after development was less than 80% was evaluated as ×.

[Method for Evaluating Heat Resistance] The obtained glass substrate with a cured film was reheated at 250 ° C for 1 hour, and then the film thickness before heating and the film thickness after heating were measured, and the residue was calculated by the following calculation formula. Membrane rate. The film thickness was measured using P-16. The case where the residual film rate after heating was 95% or more was evaluated as ○, and the case where the residual film ratio after heating was less than 95% was evaluated as ×. Residual film rate = (film thickness after heating / film thickness before heating) × 100

[Evaluation Method of Transparency] In the obtained glass substrate with a cured film, the ultraviolet light-visible near-infrared spectrophotometer (trade name; V-670, Japan Optical Co., Ltd.) was used to measure the wavelength of only the cured film to be 400 nm. Transmittance under the light. The case where the transmittance was 95% or more was evaluated as ○, and the case where the transmittance was less than 95% was evaluated as ×.

[Preparation of substrate for analytical evaluation] Next, the photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and prebaked on a hot plate at 100 ° C for 80 seconds. Next, in the air, a mask having a hole and a line pattern having a width of 20 μm was interposed, and exposure was performed using a proximity exposure machine TME-150PRC with an exposure gap of 100 μm. The exposure amount was measured by an integrated light meter UIT-102 and a light receiver UVD-365PD to be 30 mJ/cm ² . The exposed coating film was subjected to liquid-coating development at 27 ° C for 40 seconds using a buffer solution of sodium carbonate x sodium hydrogencarbonate, and then the unexposed portion was removed. The developed coating film was washed with pure water for 20 seconds, and then dried by a hot plate at 100 ° C for 2 minutes. Further, post-baking was carried out in an oven at 230 ° C for 30 minutes to obtain a glass substrate having a patterned cured film having a film thickness of 1.5 μm.

Regarding the cured film obtained as described above, the properties were evaluated for the analytical properties.

[Analytical Evaluation Method 1] The obtained glass substrate with a patterned cured film was observed with a 1,000-fold optical microscope, and the resolution of the hole and the line pattern corresponding to the mask size of 20 μm was evaluated. The case where the hole and the line pattern were analyzed was evaluated as "○", and the unresolved case was evaluated as "X".

[Analytical evaluation method 2] The cross section of the hole portion corresponding to the cover size of 20 μm of the obtained glass substrate with a patterned cured film was observed by SEM, and the equivalent substrate shown in FIG. 1 was measured. The diameter AB of the bottom portion of the surface and the aperture CD at a portion of 0.5 μm from the bottom surface of the substrate surface in the vertical direction, and the cured film and the hem near the substrate were evaluated based on the value of CD/AB. The smaller the value of CD/AB, the more the hem is suppressed. The value of less than 1.1 was evaluated as "○", and the value of 1.1 or more was evaluated as "x".

[Production of Flatness Evaluation Substrate] Next, the photosensitive composition was spin-coated at 900 rpm for 10 seconds on a pigment dispersion color filter (hereinafter abbreviated as CF) substrate using a resin black matrix having a maximum step difference of about 0.8 μm. On the hot plate at 100 ° C, prebaking was performed for 80 seconds. Next, exposure was performed using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.). The exposure amount was measured by using an integrated light meter UIT-102 (trade name; oxtail (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; oxtail (USHIO) Co., Ltd.) to be 30 mJ/cm. ² . The coating film after exposure was subjected to liquid-coating development at 27 ° C for 40 seconds using a buffer solution of sodium carbonate x sodium hydrogencarbonate, and then the coating film was washed with pure water for 20 seconds, and then subjected to a hot plate at 100 ° C for 2 minutes. dry. Further, post-baking was carried out in an oven at 230 ° C for 30 minutes to obtain CF having a cured film having a film thickness of 1.5 μm.

Regarding the cured film obtained as described above, the properties were evaluated for flatness.

[Evaluation method of flatness] The obtained color filter substrate with a cured film was measured using a step, surface roughness, and fine shape measuring device (trade name; P-16, KLA TENCOR Co., Ltd.) The step of the surface of the cured film. The case where the maximum value of the step difference between the R, G, and B pixels including the black matrix (hereinafter abbreviated as the maximum step) is less than 0.16 μm is evaluated as ○, and the case where 0.16 μm or more is evaluated as × is evaluated.

[Example 2 to Example 10] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) shown in Table 1, and a photosensitive composition was obtained. Further, regarding the abbreviations of the additives in Tables 1 to 4, M-520 and M-402 represent a compound having a polymerizable double bond, Aronix M-520, and Aronix M-402 ( All are trade names; East Asia Synthetic Co., Ltd.), NCI-930 stands for photopolymerization initiator ADEKA ARKLS NCI-930 (trade name; ADEKA) VG3101L stands for epoxy compound TECHMORE VG3101L (trade name; Printec), TMA stands for epoxy hardener trimellitic anhydride, and S510 stands for coupling agent Sila-Ace S510 (trade name; JC), AO-60 stands for antioxidant ADX STAB AO-60 (trade name; ADEKA), F- 556 denotes a surfactant, Megafac F-556 (trade name; Di Ai Sheng (DIC) Co., Ltd.), MMP denotes a solvent methyl 3-methoxypropionate, and PGMEA denotes a solvent propylene glycol monomethyl ether acetate , EDM stands for diethylene glycol methyl ethyl ether.

Table 1 Unit [g]

[Examples 11 to 19] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 2 to obtain a photosensitive composition.

Table 2 Unit [g]

[Comparative Example 1 to Comparative Example 9] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 3 to obtain a photosensitive composition. table 3 Unit [g]

[Comparative Example 10 to Comparative Example 18] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 4 to obtain a photosensitive composition. Table 4 Unit [g]

In the following, the evaluation results of the cured films of Examples 1 to 10 are collectively shown in Table 5, and the evaluation results of the cured films of Examples 11 to 19 are collectively shown in Table 6, and Comparative Example 1 is shown. The evaluation results of the cured film of Comparative Example 9 are collectively shown in Table 7, and the evaluation results of the cured films of Comparative Examples 10 to 18 are collectively shown in Table 8. table 5

Table 6

Table 7

Table 8

According to the results shown in Tables 5 to 8, the cured films of Examples 1 to 10 were excellent in heat resistance, transparency, and flatness, and further balanced in all aspects including the residual film ratio after development and the resolution. The cured films of Examples 11 to 19 were inferior to Examples 1 to 10 except that the average value of the flatness was slightly large. On the other hand, all the evaluation items of the cured films of Comparative Examples 1 to 18 were not "○". The cured films of Comparative Example 1 and Comparative Example 10 were inferior in the analytical properties, and the cured films of Comparative Examples 2 and Comparative Examples 11 were all dissolved after development. In the cured films of Comparative Example 3 and Comparative Example 12, the residual film ratio after development was low, and the hem of the cured film was also observed. The cured films of Comparative Example 4, Comparative Example 6, Comparative Example 8, Comparative Example 13, Comparative Example 15, and Comparative Example 17 were excellent in resolution, but the residual film ratio after development was inferior. Further, in the cured films of Comparative Example 5, Comparative Example 7, Comparative Example 9, Comparative Example 14, Comparative Example 16, and Comparative Example 18, there was no problem in the residual film ratio after development, but the resolution was poor. As described above, in the case where the following polyester phthalic acid is used, and the ratio of [the content of the photopolymerization initiator/content of the molecular weight modifier] is within the scope of the invention, all the characteristics can be satisfied, the polyester Proline is a reaction product derived from a raw material containing tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential components. [Industrial availability]

The cured film obtained from the photosensitive composition of the present invention is excellent in heat resistance, transparency, flatness, and resolution as an optical material, and can be used as a color filter, an LED light-emitting element, and light from this point of view. A protective film of various optical materials such as a receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

AB‧‧‧ bottom diameter of the substrate surface
CD‧‧‧Aperture in the vertical direction at a distance of 0.5 μm from the bottom surface of the substrate surface

Fig. 1 is a scanning electron microscope photograph obtained by photographing a cross section of a hole of a glass substrate having a patterned cured film.

Claims (22)

A photosensitive composition comprising a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent, and a molecular weight modifier; the photosensitivity The composition is characterized in that the polyester proline is derived from a tetracarboxylic dianhydride containing X mole, a diamine of Y mole, and a Z molar ratio in a ratio established by the following formula (1) and formula (2). The reaction product of the raw material of the polyvalent hydroxy compound of the ear has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); and a compound having a polymerizable double bond contains two or more per molecule. Polymerizable double bond; the epoxy compound contains two to ten epoxy groups per molecule, and the weight average molecular weight is less than 3,000; and the total of the compound having a polymerizable double bond with respect to 100 parts by weight of the polyester phthalic acid The amount is from 20 parts by weight to 300 parts by weight, the total amount of the epoxy compound is from 20 parts by weight to 200 parts by weight, and the content of the photopolymerization initiator is more than 5.0 times and less than 30 times the content of the molecular weight modifier; ≦Z/Y≦8.0 ······· 1) 0.2 ≦ (Y + Z) /X≦5.0 ··· (2) In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is a two-NH ₂ removal from the diamine. The resulting residue, R ^{3 ,} is a residue obtained by removing two -OH from a polyvalent hydroxy compound. The photosensitive composition according to claim 1, wherein the molecular weight modifier is selected from the group consisting of thiols, xanthogens, anthraquinones, and 2,4-diphenyl-4-methyl-1-pentene. More than one of them. The photosensitive composition according to claim 1, wherein the molecular weight modifier is naphthoquinone. The photosensitive composition according to claim 1, wherein the molecular weight modifier is 2-hydroxy-1,4-naphthoquinone. The photosensitive composition according to claim 1, wherein the raw material component of the polyester phthalic acid further comprises a monohydroxy compound. The photosensitive composition according to claim 5, wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl- One or more of 3-hydroxymethyloxetane. The photosensitive composition according to any one of claims 1 to 5, wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000. The photosensitive composition according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3 One or more of 4-butane tetracarboxylic dianhydride and ethylene glycol bis(hydrogen trimellitate). The photosensitive composition according to any one of claims 1 to 5, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-amine) One or more of phenoxy)phenyl]indoles. The photosensitive composition according to any one of claims 1 to 5, wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentane Alcohol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl And one or more of tris(2-hydroxyethyl) isocyanurate. The photosensitive composition according to any one of claims 1 to 5, wherein the compound having a polymerizable double bond contains 50% by weight or more based on the total weight of the compound having a polymerizable double bond. Selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isomeric cyanuric acid ethylene oxide modified triacrylate, and polyacid modified (meth)acrylic acid oligomerization One or more of them. The photosensitive composition according to any one of claims 1 to 5, wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxy Cyclohexylmethyl ester, 1-methyl-4-(2-methyloxacyclopropyl)-7-oxabicyclo[4.1.0]heptane, 2-[4-(2,3-epoxypropane Oxy)phenyl]-2-[4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane with 1,3-bis[4 -[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1- Mixture of methylethyl]phenyl]ethyl]phenoxy]-2-propanol, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1 , 1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether, 1,3-bis(oxopropylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 One or more of 1,2-epoxy-4-(2-oxopropyl)cyclohexane adducts of 2-bis(hydroxymethyl)-1-butanol. The photosensitive composition according to any one of claims 1 to 5, wherein the photopolymerization initiator is selected from the group consisting of an α-aminophenylalkylketone system, a mercaptophosphine oxide system, and an anthracene. One or more of the ester photopolymerization initiators. The photosensitive composition according to any one of claims 1 to 5, wherein the epoxy hardener is selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole More than one of them. The photosensitive composition according to claim 5, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1, 2, 3, More than one of 4-butane tetracarboxylic dianhydride; diamine is 3,3'-diaminodiphenyl hydrazine; polyvalent hydroxy compound is 1,4-butanediol; monohydroxy compound is benzyl alcohol; The compound of the polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified (meth)acrylic oligomer; light relative to the total weight of the photopolymerization initiator The polymerization initiator contains 50% by weight or more of 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzylidenehydrazide), ethyl ketone, 1 -[9-ethyl-6-(2-methylbenzhydryl)-9-oxazol-3-yl]-, 1-(O-ethylindenyl) and 1,2-propanedione- One or more of 1-[4-[4-(2-hydroxyethoxy)phenylthio]phenyl]-2-(O-ethenylhydrazine); the epoxy compound is selected from 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) Benzene a mixture of 1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and 2-[4-(2,3-epoxypropoxy)phenyl]-2-[ One or more of 4-[1,1-bis[4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane; the epoxy hardener is selected from the group consisting of trimellitic anhydride and 2 One or more of undecyl imidazole; the molecular weight modifier is 2-hydroxy-1,4-naphthoquinone, and the content of the photopolymerization initiator is 5.0 times or less than 30 times the content of the molecular weight modifier The method contains a molecular weight modifier; and further contains one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent. A cured film obtained by the photosensitive composition according to any one of claims 1 to 15. A color filter using the cured film described in claim 16 as a protective film. A display element using the color filter of claim 17 of the patent application. A solid-state photographic element using the color filter of claim 17 of the patent application. A display element using the cured film as described in claim 16 as a transparent insulating film formed between the thin film transistor and the transparent electrode. A display element using the cured film as described in claim 16 as a transparent insulating film formed between the transparent electrode and the alignment film. A light-emitting diode illuminant using the cured film described in claim 16 as a protective film.