TW201837603A - Photosensitive compositions and application thereof capable of forming a cured film which is excellent in transparency, heat resistance, chemical resistance, flatness, resolution, and chemical resistance - Google Patents

Abstract

The present invention relates to a photosensitive composition which includes a polyester phthalic acid (A), a compound (B) having a polymeric double bond, a photopolymerization initiator (C), an epoxy group-containing polymer (D) having a weight average molecular weight of 3,000 to 50,000, an epoxy compound (E) containing 2 to 10 epoxy groups per molecule and having a weight average molecular weight of less than 3,000, an epoxy hardener (F) and a molecular weight modifier (G). The photosensitive composition of the present invention does not require an organic solvent having a high polarity, and can form a cured film which is excellent in transparency, heat resistance, chemical resistance, flatness, resolution, and chemical resistance and can be suitably used for electronic parts.

Description

Photosensitive composition and application

The present invention relates to an insulating material in an electronic part, a passivation film, a buffer coating film, an interlayer insulating film, or a planarizing film in a semiconductor device, or an interlayer insulating film or a protective film for a color filter in a display element. The photosensitive composition used in the formation. Furthermore, this invention relates to the transparent film formed using the said photosensitive composition, and an electronic component provided with the said film.

In the manufacturing steps of elements such as display elements such as flat panel displays, various chemicals such as organic solvents, acids, and alkali solutions are sometimes processed, or when the wiring electrodes are formed by sputtering, the surface is partially grounded. Heating to high temperature. Therefore, a surface protection film may be provided for the purpose of preventing deterioration, damage, and deterioration of the surface of the element. These protective films are required to have characteristics that can withstand various processes in the general manufacturing steps described above. Specifically, transparency, flatness, light resistance, scratch resistance, water resistance, adhesion to base substrates such as glass, and heat resistance, solvent resistance, acid resistance, and alkali resistance are required. Chemical properties.

In addition, in recent years, thinner and lighter touch panels have been required, and along with this, insulating materials have not only required various characteristics such as adhesion to the substrate, transparency, flatness, and heat resistance, which were previously required. Moreover, it is required to have a developability that can be accurately formed without a gap between the electrodes. In addition, in the case of undergoing one or more steps of forming an electrode by indium tin oxide (ITO) evaporation and partial etching to form an electrode, resistance to an ITO etching solution is also required.

The type of the curable composition used to form these protective films or insulating films can be roughly classified into a photosensitive composition and a thermosetting composition. Since the thermosetting composition is completely hardened by high-temperature heating during film formation, even if heated to a high temperature in the subsequent steps, less volatile components are generated and the heat resistance is excellent. A thermosetting protective film material having such excellent characteristics includes a polyester amidate composition (for example, refer to Patent Document 1). However, the thermosetting composition cannot form scribe lines during panel division, and a large amount of fine particles of the protective film are generated. Therefore, a high degree of panel cleaning step is required thereafter.

On the other hand, the photosensitive composition contains a polymer or oligomer or monomer having a photopolymerizable group and a photopolymerization initiator, and causes a chemical reaction due to the energy of light represented by ultraviolet rays, and is cured. The photosensitive composition can easily form, for example, a scratch line for manufacturing a panel, and therefore has advantages such as not generating fine chips of the protective film. On the other hand, it is similar to a protective film formed of a thermosetting composition. In contrast, the heat resistance of a protective film formed of a general photosensitive composition is insufficient.

In recent years, a demand for a protective film that requires heat resistance, solvent resistance, and chemical resistance has gradually increased, and a demand for a protective film having a fine pattern shape has also gradually increased. Accordingly, a photosensitive composition capable of forming a protective film excellent in heat resistance, solvent resistance, and chemical resistance and capable of forming a fine pattern has been sought.

A photosensitive composition capable of forming a protective film having very excellent heat resistance includes a polyfluorene imide precursor composition (for example, refer to Patent Document 2) and a soluble polyfluorene imine composition (for example, refer to Patent Document 3). . However, even in any photosensitive composition, the organic solvent that can dissolve the obtained polyimide precursor composition or the soluble polyimide composition is limited, and an organic solvent having a very high polarity is also required.

Examples of highly polar organic solvents that dissolve the polyfluorene imide precursor composition and the soluble polyfluorene imide composition include pyrrolidone-based, fluorene-based, methylformamide-based, acetamide-based, phenol-based, tetrahydrofuran, Oxane, γ-butyrolactone, etc.

In particular, when these photosensitive compositions are used as protective films for color filters, if these polar organic solvents are included, the color filter layer which penetrates into the substrate, such as pigments or dyes contained in pixels It is difficult to produce a high-quality display element due to the elution of coloring materials.

Examples of the use of a photosensitive composition for a protective film of a color filter include Patent Literature 4 and Patent Literature 5. However, the inventors intend to use the photosensitive composition described in these patent documents to form a protective film. As a result, the pattern formed is not fully satisfactory, but further improvement is expected.

When a photosensitive composition is used for a protective film of an ITO electrode in a multilayer wiring substrate, resistance to an ITO etching solution is required. However, Patent Document 5 does not mention resistance to an ITO etching solution.

In addition, regardless of the photosensitive composition and the thermosetting composition, it is required that these curable compositions have excellent coatability on a base substrate. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2008-156546 [Patent Literature 2] Japanese Patent Laid-Open No. 59-068332 [Patent Literature 3] Japanese Patent Laid-Open No. 2002-003516 [Patent Literature 4] Japanese Patent Laid-Open No. 2011-090275 [ Patent Literature 5] Japanese Patent Laid-Open No. 2016-103010

[Problem to be Solved by the Invention] An object of the present invention is to provide a photosensitive composition that does not require an organic solvent having a high polarity and forms a cured film having excellent transparency, heat resistance, flatness, resolvability, and chemical resistance. In addition, a cured film formed from the photosensitive composition is provided, and an electronic component having the cured film is further provided. [Technical means to solve the problem]

The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that the above-mentioned object can be achieved by the following composition and a cured film obtained by curing the composition, and have completed the present invention. The composition contains polyester sulfamic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy hardener, and a molecular weight adjuster. It is obtained by the reaction of a compound of an anhydride, a diamine, and a polyhydroxy compound. The present invention includes the following configurations.

[1] A photosensitive composition comprising a polyester amidate (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), and a polymer having an epoxy group (D ), An epoxy compound (E), an epoxy hardener (F), and a molecular weight adjuster (G); the photosensitive composition is characterized in that the polyester amidate (A) Tetracarboxylic dianhydride, Y mole diamine, and Z mole polyhydroxy compound are obtained by reacting at a ratio where the relationship of the following formula (1) and formula (2) is established, and include the following formula (3 A structural unit represented by) and a structural unit represented by the following formula (4); the compound (B) having a polymerizable double bond includes two or more polymerizable double bonds per molecule; and the ring having a ring The weight average molecular weight of the polymer (D) having an oxygen group is 3,000 to 50,000; the epoxy compound (E) contains 2 to 10 epoxy groups per molecule, and the weight average molecular weight is less than 3,000; relative to 100 parts by weight of the polyester amidine (A), and of the compound (B) having a polymerizable double bond The amount is 20 parts by weight to 300 parts by weight, and the total amount of the epoxy group-containing polymer (D) and the epoxy compound (E) is 20 parts by weight to 200 parts by weight; the photopolymerization initiator The content of (C) is more than 5.0 times and less than 30 times of the content of the molecular weight modifier (G); 0.2≤Z / Y≤8.0 ······· (1) 0.2≤ (Y + Z) /X≤5.0···(2) In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is obtained by removing two -NH ₂ from a diamine. R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound.

[2] The photosensitive composition according to the item [1], wherein a raw material component of the polyester amidate further contains a monohydroxy compound.

[3] The photosensitive composition according to item [2], wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3- One or more of ethyl-3-hydroxymethyloxetane.

[4] The photosensitive composition according to any one of [1] to [3], wherein a weight average molecular weight of the polyester amidine (A) is 1,000 to 200,000; the tetracarboxylic acid The dianhydride is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [ One of bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitic acid ester) Above; the diamine is one or more selected from 3,3'-diaminodiphenylphosphonium and bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is Selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, One or more of 2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and tris (2-hydroxyethyl) isocyanurate; with respect to the polymerizable bis The total weight of the compound having a bond, and the compound (B) having a polymerizable double bond contains at least 50% by weight selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylic acid One or more of pentaerythritol triacrylate, ethylene isocyanate-modified triacrylate, and polyacid-modified (meth) acrylic acid oligomer; the photopolymerization initiator (C) is selected One or more selected from the group consisting of an α-aminobenzoyl ketone system, a fluorenyl phosphine oxide system, and an oxime ester system photopolymerization initiator; and the polymer (D) having an epoxy group An epoxy group-containing copolymer of a reaction product of a mixture of a radically polymerizable monomer (d1) and a radically polymerizable monomer (d2) other than (d1); and the epoxy hardener (F) It is one or more selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole.

[5] The photosensitive composition according to [4], wherein the radically polymerizable monomer (d1) having an epoxy group is selected from glycidyl (meth) acrylate and (meth) acrylic acid One or more of 3,4-epoxycyclohexyl methyl ester and 4-hydroxybutyl (meth) acrylate glycidyl ether; a radically polymerizable monomer (d2) other than (d1) containing a difunctional (methyl) More than one type of acrylate.

[6] The photosensitive composition according to any one of the items [1] to [5], wherein the molecular weight adjuster (G) is selected from mercaptans and xanthogen Or more, one or more of quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene.

[7] The photosensitive composition according to [5], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2 One or more of 3,4-butanetetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenylphosphonium; the polyhydroxy compound is 1,4-butanediol; The monohydroxy compound is benzyl alcohol; the compound (B) having a polymerizable double bond is one selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyacid-modified (meth) acrylic acid oligomer Above; the difunctional (meth) acrylate is selected from ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (methyl) One or more of acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecanedimethanol di (meth) acrylate; The total weight of the photopolymerization initiator (C), the photopolymerization initiator (C) contains more than 50% by weight selected from 1,2-octanedione, 1- [4- (phenylthio) phenyl ]-, 2- (O-benzylideneoxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) ) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylsulfide One or more of the groups] phenyl] -2- (O-acetamidooxime); the epoxy hardener (F) is one or more selected from trimellitic anhydride and 2-undecylimidazole; and The photosensitive composition further contains, as a solvent, one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate.

[8] The photosensitive composition according to any one of [1] to [7], wherein the molecular weight modifier (G) is one or more selected from naphthoquinones and hydroquinones .

[9] A cured film obtained from the photosensitive composition according to any one of the items [1] to [8].

[10] A color filter having a cured film according to [9] as a transparent protective film.

[11] A display element using the color filter according to [10].

[12] A solid-state imaging element using the color filter according to [10].

[13] A display element using the cured film according to [9] as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[14] A display element using the cured film according to [9] as a transparent insulating film formed between a TFT and an alignment film.

[15] A light emitting diode (Light Emitting Diode, LED) light emitting body using the cured film according to item [9] as a protective film.

[16] An interlayer insulating film having the cured film according to [9] as a transparent protective film. [Effect of the invention]

The photosensitive composition according to a preferred embodiment of the present invention is a material that does not require an organic solvent having a high polarity and can form a cured film excellent in transparency, heat resistance, flatness, resolvability, and chemical resistance. When used as a color filter protective film for a display element, display quality and reliability can be improved. It can also be used as a protective film and a transparent insulating film of various optical materials.

1. Photosensitive composition The photosensitive composition of the present invention is a compound (B) containing polyester amidate (A), two or more polymerizable double bonds per molecule, and a photopolymerization initiator ( C), epoxy-containing polymer (D), epoxy compound (E), epoxy hardener (F) containing 2 to 10 epoxy groups per molecule and having a weight average molecular weight of less than 3,000 And a molecular weight modifier (G), the polyester amido acid (A) is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components. The photosensitive composition is characterized in that the compound (B) having a polymerizable double bond is 20 to 300 parts by weight with respect to 100 parts by weight of the polyester amido acid (A). The total amount of the polymer (D) and the epoxy compound (E) is 20 to 200 parts by weight, and the content of the photopolymerization initiator (C) is more than 5.0 times and less than the content of the molecular weight modifier (G). 30 times. In addition, the photosensitive composition of the present invention may further contain components other than those described above within a range in which the effects of the present invention are obtained.

1-1. Polyesteramidic acid (A) Polyesteramidic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw material components. More specifically, the reaction is performed by reacting X mol tetracarboxylic dianhydride, Y mol diamine, and Z mol polyhydric hydroxy compound at a ratio where the relationship of the following formula (1) and formula (2) is established. obtain. 0.2≤Z / Y≤8.0 ······ (1) 0.2≤ (Y + Z) /X≤5.0··· (2)

The polyester amidine 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 a polyhydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required for the synthesis of polyester glutamic acid. The solvent can be left as it is, and it can be made into a liquid or gel-like photosensitive composition in consideration of operability. Alternatively, the solvent can be removed to make it possible to consider handling. Solid composition. Moreover, the synthesis | combination of polyester glutamic acid may contain one or more types of compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material as needed, among these, it is preferable to contain a monohydroxy compound. Moreover, the synthesis | combination of polyester glutamic acid can also contain other compounds as a raw material as needed within the range which does not impair the objective of this invention. Examples of such other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride In the present invention, a material used to obtain polyester amidate is tetracarboxylic dianhydride. Specific examples of the preferred tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2 ', 3, 3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid Dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis ( 3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitic acid ester) (trade name: TMEG- 100, New Japan Physical and Chemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, and ethyl acetate Alkyltetracarboxylic dianhydride. One or more of these may be used.

Among these tetracarboxylic dianhydrides, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 3,3', 4,4'-dicarboxylic acid which impart good transparency to the cured film are more preferred. Phenyl 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-butanetetracarboxylic dianhydride.

1-1-2. Diamine In the present invention, a diamine is used as a material for obtaining polyester amidate. Specific examples of preferred diamines include 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, and bis [4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl ] 碸, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] 碸, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] fluorene, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these may be used.

Among these diamines, 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene which give good transparency to the cured film are more preferable, and 3 is particularly preferable. , 3'-diaminodiphenylphosphonium.

1-1-3. Polyhydroxy compound In the present invention, the material used to obtain polyester amidate is a polyhydroxy compound. Specific examples of preferred polyhydroxy 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, 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 Diol, 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-octantriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1 , 10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, Tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) fluorene), bis Phenol F (bis (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxybicyclo Group, diethanolamine, and triethanolamine. One or more of these may be used.

Among these polyhydric hydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7, which have good solubility in the reaction solvent, are more preferable. -Heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and tris (2-hydroxyethyl isocyanurate) Ester), and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are particularly preferred.

1-1-4. Monohydroxy Compound In the present invention, a monohydroxy compound can be used as a material for obtaining polyester amidate. By using a monohydroxy compound, the storage stability of a 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 monoethyl ether, diethylene glycol monomethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethyl benzyl methanol benzyl carbinol). One or more of these may be used.

Among these monohydroxy compounds, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility of the polyester amidate formed using these monohydroxy compounds with a polymer having an epoxy group, an epoxy compound, and an epoxy hardener, or the photosensitive composition in a color filter For coating properties on optical sheets, benzyl alcohol is particularly preferably used as the monohydroxy compound.

The reaction is preferably carried out with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, and containing 0 to 300 parts by weight of a monohydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer In addition, the polyester amidine used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the raw material. It is preferable to perform transparency as described above because the transparency of the cured film can be improved. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. As for the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5 to 4, preferably 1 to 3. Furthermore, 1 or 2 is more preferable, and 1 is especially preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Chemical Co., Ltd.). Among these commercially available products, SMA1000P, which has excellent heat resistance and alkali resistance of the cured film, is particularly preferred.

The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More preferably, it is 10 to 300 parts by weight.

1-1-6. In the synthesis of polyester sulfamic acid, a silicon-containing monoamine may also include other raw materials other than those mentioned above as raw materials, as long as the purpose of the present invention is not impaired. Examples include silicon-containing monoamines.

Specific examples of the preferred silicon-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropylmethyldiamine. Methoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethyl Oxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane , M-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these may be used.

Among these silicon-containing monoamines, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which improve the acid resistance of the cured film, are more preferred from the viewpoint of acid resistance and compatibility. In other words, 3-aminopropyltriethoxysilane is particularly preferred.

The silicon-containing monoamine is preferably contained in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound. More preferably, it is 5 to 200 parts by weight.

1-1-7. Solvents used in the synthesis reaction of polyester glutamic acid Specific examples of the solvents used in the synthesis reaction to obtain polyester glutamic acid include diethylene glycol dimethyl ether, Ethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ether is preferable.

1-1-8. Method for synthesizing polyester amidate The method for synthesizing polyester amidate used in the present invention is to make tetracarboxylic dianhydride X mole, diamine Y mole, And Z Mol reaction of polyhydroxy compounds. At this time, X, Y, and Z are preferably set to a ratio in which the relationship of the following formula (1) and formula (2) is established between these X, Y, and Z. When the content is within this range, the solubility of the polyester amidino acid in the solvent is high, and the coatability of the composition is improved. As a result, a cured film having excellent flatness can be obtained. 0.2≤Z / Y≤8.0 ······· (1) 0.2≤ (Y + Z) /X≤5.0·· (2) In formula (1), preferably 0.7≤Z / Y≤7.0, more Preferably 1.0 ≦ Z / Y ≦ 5.0. In the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferred, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferred.

It can be considered that the polyester amidine used in the present invention is produced in excess at the terminal under the reaction conditions described above under conditions where X is excessively used over Y + Z than molecules having an amine group or a hydroxyl group at the terminal. Molecules with acid anhydride group (-CO-O-CO-). When reacting with such a monomer structure, in order to react with an acid anhydride group at the molecular terminal to esterify the terminal, the monohydroxy compound may be added as necessary. The polyester glutamic acid obtained by adding a monohydroxy compound for reaction can improve compatibility with epoxy compounds and epoxy hardeners, and can improve coatability of the photosensitive composition of the present invention containing these compounds.

Moreover, when reacting with the said monomer structure, a silicon-containing monoamine may be added in order to introduce a silyl group into a terminal in order to react with the acid anhydride group of a molecular terminal. When the photosensitive composition of the present invention containing a polyester amidino acid obtained by adding a silicon-containing monoamine for reaction is used, the acid resistance of the obtained cured film can be improved. Furthermore, when reacting with the structure of the said monomer, you may add both a monohydroxy compound and a silicon containing monoamine, and react.

It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total of tetracarboxylic dianhydride, diamine, and polyhydroxy compound, since the reaction proceeds smoothly. The reaction is preferably performed at 40 ° C to 200 ° C for 0.2 hours to 20 hours.

The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, any of the following methods may be used: tetracarboxylic dianhydride, diamine, and polyhydric hydroxyl compound are simultaneously added to the reaction solvent; after diamine and polyhydroxy compound are dissolved in the reaction solvent, tetracarboxylic acid di is added Anhydride; after reacting tetracarboxylic dianhydride with a polyhydroxy compound in advance, adding a diamine to its reaction product; or after reacting tetracarboxylic dianhydride with a diamine in advance, adding a polyhydroxy compound, etc., to its reaction product.

In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyhydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added at 10 ° C. The reaction at -40 ° C is preferably from 0.1 to 6 hours. In addition, a monohydroxy compound may be added at an arbitrary point in the reaction.

The polyester sulfamic acid synthesized in the above manner includes the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and its terminal is derived from tetracarboxylic dianhydride and dicarboxylic acid as raw materials. An acid anhydride group, an amine group, or a hydroxyl group of an amine or a polyhydroxy compound, or an additive other than these compounds constitutes a terminal thereof. By including such a structure, hardenability becomes favorable.

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

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

1-2. Compound (B) having a polymerizable double bond 1-2-1. Compound having two or more polymerizable double bonds in each molecule Compounds having a polymerizable double bond used in the present invention There is no particular limitation, and compounds having two or more polymerizable double bonds per molecule are preferred. When the compound having a polymerizable double bond is from 20 parts by weight to 300 parts by weight based on 100 parts by weight of polyester amidine, the residual film rate after development is good, which is preferable.

Examples of the compound contained in the photosensitive composition of the present invention that has two or more polymerizable double bonds per molecule include ethylene glycol di (meth) acrylate and 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 (methyl Base) acrylate, epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di ( (Meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylic acid 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 di ( Base) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (methyl) Base) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, glycerol (meth) acrylate, glycerin Alcohol di (meth) acrylate, glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxytrimethyl Neopentyl glycol di (meth) acrylate, caprolactone modified hydroxytrimethyl acetate neopentyl glycol di (meth) acrylate, diglycerol tetra (meth) acrylate, diglycerin epoxy Ethane-modified acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylic acid Ester, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (methyl) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, polyacid-modified (meth) acrylic oligomer, allyl cyclohexyl di (meth) acrylate, bis ((methyl Base) propylene fluorene neopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F bis (methyl Base) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, dicyclopentyl diacrylate, polyester diacrylate, polyester triacrylate, poly Ester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, ethylene oxide modified phosphate di (meth) acrylate, ethylene oxide modified phosphate tri (meth) acrylate, epichlorohydrin modified Phthalate di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di ( (Meth) acrylic acid ester, ethylene isocyanate modified ethylene oxide diacrylate, ethylene isocyanate modified ethylene oxide triacrylate, caprolactone modified tri ((meth) acrylic acid) Ethyl] isotricyanate, (meth) acrylated isotricyanate, 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-amine Prepolymer, pentaerythritol triacrylate-isophorone diisocyanate-urethane prepolymer, dipentaerythritol pentaacrylate-hexamethylene diisocyanate-urethane prepolymer , Non-yellowing oligomeric urethane acrylate, and carboxylic acid-containing urethane acrylate-oligomer.

The compound having two or more polymerizable double bonds per molecule may be used alone, or two or more kinds may be used in combination.

From the viewpoint of heat resistance and chemical resistance of the cured film, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol are preferably used for compounds having two or more polymerizable double bonds per molecule. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid modified (meth) acrylic oligomer, isotricyanic acid ethylene oxide modified diacrylate, isotricyanate ring Oxyethylene modified triacrylate, or a mixture of these.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacrylic acid modified (meth) acrylic acid oligomer, isotricyanuric acid ring The following commercially available products can be used as the oxyethylene-modified diacrylate, the ethylene isocyanide-modified ethylene oxide triacrylate, or a mixture of these. A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; East Asia Synthesis Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronix M-306 (65% to 70% by weight), Aronix M-305 (55% 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") (both are trade names; Toa Synthetic Co., Ltd., the content ratio in parentheses is the value recorded in the catalogue of the content ratio of pentaerythritol triacrylate in the mixture) . Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% to 60% by weight), Aronix M-400 (40% by weight to 50% by weight), Aronix M-402 (30% to 40% by weight, hereinafter referred to as "M-402"), 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. Company, the content rate in parentheses is the catalog value of the content rate of dipentaerythritol pentaacrylate in the mixture). Specific examples of the polyacid-modified (meth) acrylic acid oligomer are Aronix M-510 and Aronix M-520 (both trade names; East Asia Synthesis Co., Ltd.). A specific example of the ethylene triisocyanate-modified diacrylate is Aronix M-215 (trade name; East Asia Synthesis Co., Ltd.). A specific example of a mixture of ethylene isocyanate-modified diacrylate and ethylene isocyanate-modified triacrylate is Aronix M-315 (3% by weight to 13%). % By weight, hereinafter abbreviated as "M-315") (trade name; East Asia Synthetic Co., Ltd., the content ratio in parentheses is a catalog of the content ratio of isotriethylene cyanide ethylene oxide modified diacrylate in the mixture Documented value).

1-2-2. A compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule The photosensitive 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 per molecule. If the compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule is 1 part by weight to 100 parts by weight of polyester amidate. 50 parts by weight is preferred because the resolvability is improved.

Examples of such a compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule include (meth) acrylic acid and (meth) acrylic acid. Hydroxyethyl ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) propylene succinate Ethoxyethyl ester, hexahydrophthalic acid-2- (meth) acrylic acid ethoxyethyl ester, phthalic acid-2- (meth) acrylic acid ethoxyethyl ester, phthalic acid-2 -(Meth) acryloxyethyl-2-hydroxyethyl, 4-hydroxyphenyl (meth) acrylate, anilide para- (meth) acrylate, 4-hydroxybutyl (meth) acrylate Esters, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerol mono (meth) acrylate, 3- (2-hydroxyphenyl) acrylate, and β-carboxy (meth) acrylate Ethyl ester.

Among these compounds, 4-hydroxyphenyl (meth) acrylate and anilide of p-hydroxy (meth) acrylic acid are preferred because they have better resolvability.

1-3. Photopolymerization initiator (C) The photopolymerization initiator contained in the photosensitive composition of the present invention is not particularly limited as long as it can start polymerization of the following composition. The composition Contains polyester amidate, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy hardener, and a molecular weight modifier.

Examples of the photopolymerization initiator contained in the photosensitive composition of the present invention include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and xanthone , Thiaxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2- Hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholine ) -1-acetone (for example, trade name: IRGACURE 907, BASF Japan Co., Ltd.), 2- (dimethylamino) -1- (4- (4-? (Phenolino) phenyl) -2- (phenylmethyl) -1-butanone (for example, trade name: IRGACURE 369, BASF Japan Co., Ltd.), 4-dimethyl Ethylaminobenzoate, 4-dimethylaminoisobenzoate, 4,4'-bis (tert-butylperoxycarbonyl) benzophenone, 3,4,4'-tris (tertiary Butylperoxycarbonyl) di Methyl ketone, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylidene oxime) (for example, trade name: IRGACURE) OXE01 , BASF Japan Co., Ltd.), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl]-, 1- ( O-acetylamoxime) (eg, trade name: IRGACURE OXE02, BASF Japan Co., Ltd.), IRGACURE OXE03 (trade name; BASF Japan) Co., Ltd.), IGACURE OXE04 (trade name; BASF Japan Co., Ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) Phenylthio] phenyl] -2- (O-acetylamoxime) (for example, trade name: Adeka Arkls NCI-930, ADEKA Corporation), Adeka Arkls NCI-831 (trade name; ADEKA Co., Ltd.), Adeka Optomer N-1919 (trade name; Adeco (ADEKA) Co., Ltd.), 2,4,6-trimethylbenzylidene di Phosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -triazine, 2- (3 ', 4'-dimethoxystyryl ) -4,6-bis (trichloromethyl) -mesytriazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -mesityl Azine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6- Bis (trichloromethyl) -mesytriazine, 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -mesytriazine, 1, 3-bis (trichloromethyl) -5- (2'-chlorophenyl) -mesytriazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl)- Mesazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 ' -Carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2, 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetrabenzene Base-1 , 2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2-methyl-2-morpholinopropylamido)- 9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, and bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium and the like.

The photopolymerization initiator may be used alone or as a mixture of two or more. Among the photopolymerization initiators, in terms of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, α-aminobenzoyl ketone, fluorenyl phosphine oxide, and oxime ester based photopolymerization initiators are preferred. Agent. In this specification, a film obtained by pre-drying (pre-baking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing, or other methods is referred to as a "coating film". After the coating film is subjected to subsequent steps of exposure, development, cleaning, and drying, it is formed into a cured film by formal calcination (post-baking). In this specification, the thin films in the steps from the pre-heating to the drying are referred to as "coating films", and are expressed, for example, as "coating films during exposure" and "coating films after development". What stage of the film coating step?

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 preferred. -(O-benzylidene oxime) or 1,2-propionedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidine The oxime) is 20% by weight or more based on the total weight of the photopolymerization initiator. Moreover, if it is 50 weight% or more, it is more preferable. The photopolymerization initiator may also contain only 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylideneoxime), or 1,2-propanedione Ketones, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetamidooxime).

1-4. Polymer having epoxy group (D) The weight average molecular weight of the polymer having an epoxy group used in the present invention is 3,000 or more. By adding an epoxy compound to the photosensitive composition of the present invention, the heat resistance, solvent resistance, and chemical resistance of the cured film can be improved.

The polymer having an epoxy group can be obtained by reacting glycidyl (meth) acrylate with another radical polymerizable monomer. The use of such a copolymer having an epoxy group is preferred because the transparency of the cured film obtained from the photosensitive composition is increased, and the decrease in transparency in the UV ozone treatment step or the ultraviolet exposure step is suppressed. From the viewpoints of flatness, heat resistance, and solvent resistance, glycidyl (meth) acrylate preferably accounts for 50% to 99% by weight of all monomers constituting the copolymer having an epoxy group.

Examples of the other radical polymerizable monomer include a monofunctional (meth) acrylate, a difunctional (meth) acrylate, and a trifunctional or higher polyfunctional (meth) acrylate. In order to improve the heat resistance and chemical resistance of the cured film obtained from the photosensitive composition, it is preferable to use a trifunctional or higher polyfunctional (meth) acrylate. On the other hand, in order to improve the flatness and composition of the cured film For compatibility of the polyester amidate in the product, it is preferable to use a monofunctional (meth) acrylate. However, the heat resistance, solvent resistance of the cured film, the flatness of the cured film, and the compatibility with the polyester amidate in the composition tend to be compromised. Therefore, in order to exert these properties in a balanced manner, it is preferable to use two solvents. Functional (meth) acrylate.

Preferred examples of the difunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 1,4-butanediol di (meth) acrylic acid. Esters, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate. These examples are preferable because the epoxy group-containing polymer obtained by reacting with glycidyl (meth) acrylate has good compatibility with polyester amidate. From the viewpoints of flatness, heat resistance, and chemical resistance, it is preferable to contain 1 to 30 parts by weight of a difunctional (meth) acrylate in all of the monomers to be a raw material of the polymer having an epoxy group. .

The polymer having an epoxy group may contain, as a raw material component, a radical polymerizable monomer other than glycidyl (meth) acrylate and a difunctional (meth) acrylate. From the viewpoint of exhibiting the characteristics of the other radically polymerizable monomer without impairing the effects of the present invention, it is preferable to contain 0 to 20% by weight of such other radically polymerizable monomer. As the other radical polymerizable monomer, the above-mentioned monofunctional (meth) acrylate and trifunctional or higher polyfunctional (meth) acrylate can be used.

Specific examples of the monofunctional (meth) acrylate are methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) Dicyclopentyl acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Ester, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, ( M-phenoxybenzyl methacrylate, and tetrahydrofurfuryl (meth) acrylate.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate are trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane ethoxy triacrylate, and trimethylol Propane propoxy triacrylate, ethoxylated isotricyanate triacrylate, ε-caprolactone modified tri- (2-propenyloxyethyl) isotricyanate, glyceryl ethoxylate Triacrylate, glyceryl propoxy triacrylate, di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate.

The other radical polymerizable monomers may be one kind or two or more kinds.

The weight average molecular weight of the epoxy group-containing polymer obtained by reacting glycidyl (meth) acrylate and difunctional (meth) acrylate as an essential raw material component is preferably 3,000 to 50,000, and more preferably 3,000 to 20,000. . When the molecular weight is in these ranges, sufficient resolution, flatness, heat resistance, and chemical resistance can be obtained.

1-4-1. The solvent used in the synthesis reaction of the polymer having an epoxy group is obtained by reacting a glycidyl (meth) acrylate and a difunctional (meth) acrylate as essential raw material components. The synthesis of epoxy-based polymers requires at least a solvent.

Specific examples of the solvent used in the polymerization reaction to obtain a polymer having an epoxy group include diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, and diethylene glycol. Monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone , N-methyl-2-pyrrolidone, and N, N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ether are preferable.

These solvents may be used alone or in the form of a mixed solvent of two or more. Moreover, if it is 30 weight% or less with respect to the total amount of a solvent, you may mix and use other solvents other than the said solvent.

1-4-2. Method for synthesizing polymer having epoxy group The method for synthesizing polymer having epoxy group is not particularly limited, but radical polymerization in a solution using a solvent is preferred. If a reaction solvent of 100 parts by weight or more is used with respect to 100 parts by weight of the total of glycidyl (meth) acrylate, difunctional (meth) acrylate, and other radical polymerizable monomers used as necessary, The reaction proceeds smoothly and is therefore preferred. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 hour to 24 hours. In addition, the polymerization may be performed under any pressure of pressure, reduced pressure, or atmospheric pressure.

For the synthesis of the polymer having an epoxy group, a known polymerization initiator can be used. Examples of the polymerization initiator include compounds that generate radicals by heat, azo-based initiators such as azobisisobutyronitrile, and peroxide-based initiators such as benzamidine peroxide. In the radical polymerization reaction, in order to adjust the molecular weight of the produced copolymer, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount.

The polymer having an epoxy group can directly leave a solvent used in the synthesis to form an epoxy compound solution in consideration of workability, and the solvent can be removed to form a solid ring in consideration of portability and the like. Oxygen compound.

1-5. Epoxy compound (E) The epoxy compound used in the present invention contains 2 to 10 epoxy groups per molecule, and the weight average molecular weight is less than 3,000. By adding an epoxy compound to the photosensitive composition of this invention, the heat resistance of a cured film can be improved.

Preferable examples of the epoxy compound include 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexyl methyl ester (for example, trade name: Celloxide 2021P, Daicel (Daicel) Co., Ltd.), 1-methyl-4- (2-methyloxetanyl) -7-oxabicyclo [4.1.0] heptane (for example, trade name: Xeroxide ( Celloxide) 3000, Daicel Co., Ltd.), 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4- (2 , 3-glycidoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-glycidoxy) phenyl] -1 -[4- [1- [4- (2,3-glycidoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol mixture ( For example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1 , 1-bis [4- (2,3-glycidoxy) phenyl] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether ( For example, trade name: jER 1032H60, Mitsubishi Chemical Corporation), 1,3-bis (oxetanylmethyl) -5- (2-propenyl) -1,3,5-triazine-2 , 4,6 (1H, 3H, 5H) -trione, 1,2-epoxy-4- (2-oxetanyl) group of 2,2-bis (hydroxymethyl) -1-butanol Cyclohexane adduct (for example, trade name: EHPE3150, Daicel Co., Ltd.) and the like.

When the total amount of the epoxy group-containing polymer (D) and the epoxy compound (E) is 20 parts by weight to 200 parts by weight based on 100 parts by weight of the polyester amidate (A), the flatness becomes good and Preferred.

1-6. Epoxy hardener (F) In the photosensitive composition of this invention, an epoxy hardener is used in order to improve flatness, chemical resistance, and solvent resistance. Epoxy hardeners include acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, imidazole-based hardeners, catalyst-based hardeners, and thermostable acids such as sulfonium salts, benzothiazolium salts, ammonium salts, and sulfonium salts. From the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film, the acid generator or the like is preferably an acid anhydride-based hardener or an imidazole-based hardener.

Specific examples of the acid anhydride-based hardener include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride. Etc., aromatic polycarboxylic anhydrides, such as phthalic anhydride and trimellitic anhydride. Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydrotrimellitic anhydride, which can improve the heat resistance of the cured film without impairing the solubility of the photosensitive composition in solvents, are particularly preferred.

Specific examples of the imidazole-based hardener 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 hardeners, 2-undecylimidazole, which can improve the curability of the cured film without impairing the solubility of the photosensitive composition in solvents, is particularly preferred.

1-7. Molecular weight adjuster (G) In order to suppress the increase in molecular weight due to polymerization and exhibit excellent resolution, a molecular weight adjuster is used in the photosensitive composition of the present invention. Examples of the molecular weight modifier include thiols, xanthates, quinones, hydroquinones, phenols, catechols, cresols, 2,4-diphenyl-4-methyl-1- Pentene and phenothiazine.

Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, and anthraquinone. , Hydroquinone, methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 1 2,4-dihydroxynaphthalene, 3,6-dihydroxybenzonorbornane, 4-methoxyphenol, 2,2 ', 6,6'-tetra-t-butyl-4,4'-dihydroxyl Benzene, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearate, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,4,6-tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate], 4-tert-butylcatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoacetic acid, di Methyl xanthate sulfide, diisopropyl xanthate disulfide, 2,6-di-tert-butyl-p-cresol, 4,4'-butylene bis (6-tert-butyl-m-methyl) Phenol), 4,4'-thiobis (6-tert-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, and the like.

The molecular weight adjusting agent may be used alone or in combination of two or more kinds. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred in terms of exhibiting excellent resolution.

Among molecular weight modifiers, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferred from the viewpoint of resolvability. From the standpoint of resolvability, it is preferred to include the molecular weight modifier such 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. The molecular weight adjuster is contained so that the content is 5.1 times or more and 20 times or less the content of the molecular weight adjuster. Furthermore, it is preferable to contain a molecular weight adjuster so that content of a photoinitiator may be 5.2 times more than 10 times the content of a molecular weight adjuster.

1-8. Proportions of polyester amidate, compound having polymerizable double bond, photopolymerization initiator, polymer having epoxy group, epoxy compound, epoxy hardener, and molecular weight adjusting agent The ratio of the compound having a polymerizable double bond in the sexual composition to 100 parts by weight of the polyester amidate is 20 to 300 parts by weight. When the ratio of the compound having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance, and residual film rate after development is good. The compound which has a polymerizable double bond is more preferable if it is the range of 100 weight part-300 weight part.

The ratio of the photopolymerization initiator to 2 parts by weight to 60 parts by weight with respect to 100 parts by weight of polyester amidine. From a viewpoint of the sensitivity of the coating film at the time of exposure, it is preferable that the ratio of a photoinitiator is the said range.

In the photosensitive composition of the present invention, the total ratio of the polymer having an epoxy group and the epoxy compound is 20 to 200 parts by weight based on 100 parts by weight of the polyester amidate. When the ratio of the total amount of the polymer having an epoxy group and the epoxy compound is within this range, the balance between heat resistance and flatness is good. It is more preferable that the total amount of the polymer having an epoxy group and the epoxy compound is in the range of 20 to 150 parts by weight.

The ratio of the epoxy hardener to the total amount of the epoxy-containing polymer and the epoxy compound is 100 parts by weight relative to the total amount of the epoxy-based polymer and the epoxy compound, and the epoxy hardener is 0.1 weight Parts to 60 parts by weight. For example, in the case where the epoxy curing agent is an acid anhydride-based curing agent, more specifically, it is preferable that the carboxylic acid anhydride group or carboxyl group in the epoxy curing agent is 0.1 to 1.5 times the equivalent to 1.5 times the epoxy group. Added in an equivalent manner. At this time, the carboxylic acid anhydride group is calculated at a divalent value. When the carboxylic anhydride group or the carboxyl group is added so that the carboxylic acid anhydride group or the carboxyl group becomes 0.15 times to 0.8 times equivalent, the chemical resistance is further improved, and thus it is more preferable.

1-9. Other components Various additives can be added to the photosensitive composition of the present invention to improve coating uniformity and adhesion. The main additives include solvents, photoacid generators, anionic, cationic, nonionic, fluorine or silicon surfactants, adhesion promoters, hindered phenols, hindered amines, phosphorus, sulfur Antioxidants such as compounds.

1-9-1. Solvent A solvent may be added to the photosensitive composition of the present invention. The solvent arbitrarily added to the photosensitive composition of the present invention is preferably a solvent capable of dissolving polyester amidate, a compound having a polymerizable double bond, an epoxy compound, an epoxy hardener, and the like. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and 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, 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-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 ethyl 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 ether. The solvent may be one kind of these solvents or a mixture of two or more kinds of these solvents.

1-9-2. Photoacid generator A photoacid generator may be added to the photosensitive composition of the present invention in order to exhibit excellent resolution. Examples of the photoacid generator include 1,2-quinonediazide compounds.

Specific examples of the 1,2-quinonediazide compound are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4-trihydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate (for example, trade name: NT-200, Toyo Synthetic Chemical Industry), 2,4,6-trihydroxybenzophenone-1 , 2-naphthoquinonediazide-4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3', 4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 4-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; bis (2,4-dihydroxyphenyl) methane -1,2-naphthoquinonediazide-4-sulfonate, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, bis (p-hydroxyl Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate; Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1 1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthalene Quinonediazide-5-sulfonate; bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone diazide Aza-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-tris (2,5- Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonate, 4,4 '-[1- [4- [1- [4- Hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4 '-[1- [4- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis (2,5-bis (Methyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3 ', 3'-tetra Methyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3, 3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid Acid esters; 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate, and 2,2,4-tri Methyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate.

1-9-3. Surfactant A surfactant may be added to the photosensitive composition of the present invention to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, and Polyflow No. 95 (all are trade names; Kyoeisha) Chemical Co., Ltd.), Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-164, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk ( Disperbyk) -182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all are trade names; Japan BYK Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Industry Co., Ltd.) (Surflon) S611 (trade name; AGC Seimi Chemical Co., Ltd.), Ftergent 222F, Ftergent 208G, Fudge Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, FTX-218 (all are trade names; Neo (Neos) Co., Ltd., Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Mega (Megafac) F-556, Megafac (F-558), Megafac (F-559), Megafac (R-94), Megafac (RS-75), Megafac (RS) -72-K, Megafac RS-76-NS, Megafac DS-21 (both trade names; DIC Corporation), TEGO Twin 4000, Di TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TGO Glide (T EGO Glide) 450, TEGO Rad 2200N (both trade names; Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylic acid Salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl ammonium Salt, fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether , Polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene Ethylene 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 naphthalene Ethers, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these compounds.

Among these surfactants, if selected from BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Megafac RS-72-K, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzene sulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene At least one of an ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate is preferable because the uniformity of coating of the photosensitive composition is improved.

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

1-9-4. Adhesiveness improver From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the photosensitive composition of the present invention may further include an adhesion improver. Examples of the adhesion improving agent include a coupling agent.

As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy Silane (for example, trade name: Sila-Ace S510, JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name Name: Sila-Ace S530, JNC Co., Ltd., 3-Mercaptopropyltrimethoxysilane (for example, trade name: Sila-Ace S810, Czech Republic) Enchi (JNC) Co., Ltd., a polymer of 3-glycidyloxypropyltrimethoxysilane (for example, trade name: COATOSIL MP 200, Momentive Performance Materials contract shares Co., Ltd.) and other silane-based coupling agents, aluminum coupling agents such as aluminum acetoxy aluminum diisopropoxide, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

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

Content of a coupling agent is 0.01 weight% or more and 10 weight% or less with respect to the total amount of a photosensitive composition, and since the adhesiveness of the formed cured film and a board | substrate is improved, it is preferable.

1-9-5. Macromonomer having a polymerizable double bond From the viewpoint of adhesion described in the foregoing paragraph, the photosensitive composition of the present invention may further contain a macromonomer having a polymerizable double bond.

The macromonomer having a polymerizable double bond is a reactive oligomer or polymer having a number-average molecular weight of polymerizable carbon-carbon unsaturated double bonds at the end of the molecular chain of 1,000 to 30,000.

Examples of such macromonomers available as commercially available products include: polymethylmethacrylate oligomers whose ends are methacrylated with methacrylic acid (Mn = 6,000, trade name: AA-6, East Asia Synthesis (stock )) And methacryl fluorinated poly-n-butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by Toa Sangyo Co., Ltd.). Polystyrene oligomer (Mn = 6,000, trade name: AS-6, manufactured by Toa Kosei Co., Ltd.).

1-9-6. Antioxidant The photosensitive composition of the present invention may further contain an antioxidant from the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to high temperatures.

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

The antioxidant may be used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

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

2. A cured film obtained from a photosensitive composition The photosensitive composition of the present invention can be obtained by polyester polyester amino acid, a compound having a polymerizable double bond, a polymer having an epoxy group, and a ring. Oxygen compounds, epoxy hardeners, and molecular weight modifiers are mixed, and solvents, coupling agents, surfactants, and other additives are optionally added according to the target characteristics, and these compounds are mixed and dissolved uniformly.

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

Thereafter, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. It is suitable that the amount of ultraviolet irradiation is 5 mJ / cm ² to 1000 mJ / cm ² in terms of i-rays. The photosensitive composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and becomes insoluble in an alkaline developing solution.

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

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

When the hardened film obtained in the above manner is heated, further 1) the polyamidic acid of the polyester amidamic acid is partially dehydrated and cyclized to form a iminium bond, and 2) the carboxylic acid of the polyester amidine and the epoxy resin The base polymer reacts to perform high molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be produced using the color filter. In addition to the protective film for a color filter, the cured film of the present invention is effective if used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an alignment film. Furthermore, the cured film of this invention is effective even if it is used as a protective film of LED light emitting body. [Example]

Next, the present invention will be specifically described with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to these Examples at all. In addition, the abbreviations of various materials in Tables 1-2 are demonstrated below. M-402 is a compound with a polymerizable double bond, Aronix M-402 (trade name; East Asia Synthetic Co., Ltd.), and NCI-930 is a photopolymerization initiator ADEKA Arkls ) NCI-930 (trade name; ADEKA) Co., Ltd., VG3101L is epoxy compound TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE3150 is epoxy compound EHPE3150 (brand name; Daicel Co., Ltd.), TMA is epoxy curing agent trimellitic anhydride, S510 is adhesion improver Sila-Ace S510 (brand name; JNC) Limited Company), MP 200 is the coupling agent COATOSIL MP 200 (trade name; Momentive Performance Materials contract company), AO-60 is the antioxidant ADK STAB AO- 60 (trade name; ADEKA) Co., Ltd., F-556 is the surfactant Megafac F-556 (trade name; DIC Corporation), MMP is the solvent 3- A Acid methyl ester, as a solvent of PGMEA propylene glycol monomethyl ether acetate, and, as the EDM diethylene glycol ethyl ether solvent.

Moreover, VG3101L is 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-glycidoxy)) Phenyl] ethyl] phenyl] propane (molecular weight = 593) 90% by weight and 1,3-bis [4- [1- [4- (2,3-glycidyloxy) phenyl] -1- [4- [1- [4- (2,3-Glycidoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol (Molecular weight = 1,129 ) 10% by weight of the mixture, EHPE3150 is a compound represented by the molecular formula C ₁₂₆ H ₁₉₄ O ₃₃ , and the molecular weight is 2,237 (both refer to the product safety data sheet).

First, a solution of a polyester sulfamic acid (A) containing a reaction product such as a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound, and a solution of a polymer (D) having an epoxy group are synthesized as follows (synthesis) Example 1 and Synthesis Example 2).

[Synthesis Example 1] Synthesis of polyester amidine (A) solution In a four-necked flask equipped with a stirrer, PGMEA, BT-100, and SMA1000P (trade name; benzene) subjected to dehydration purification were sequentially loaded at the following weights. Ethylene-maleic anhydride copolymer, Chuan Crude Chemical Co., Ltd.), 1,4-butanediol, and benzyl alcohol, and stirred under a stream of dry nitrogen at 125 ° C for 3 hours. 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 solution was cooled to 25 ° C, and 3,3'-diaminodiphenylsulfonium (hereinafter abbreviated as DDS (diamino diphenyl sulfone)) and PGMEA were charged at the following weights, and the reaction was performed at 20 ° C to 30 ° C for 2 hours. After stirring for 1 hour, stirring was performed 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% by weight solution of pale yellow transparent polyester amidine (A). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the polyester amidine (A) obtained was 10,000.

[Synthesis example 2] Synthesis of polymer (D) solution having epoxy group In a four-necked flask equipped with a stirrer, dehydrated and purified MMP as a polymerization solvent was charged at the following weight as an epoxy group-containing Glycidyl methacrylate of free radical polymerizable compound (a1), diethylene glycol dimethacrylate (NK Ester) 2G as other polymerizable compound (a2); trade name; Shin Nakamura Chemical Industrial Co., Ltd.), and further charged dimethyl-2,2'-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical Industries, Ltd.) as a polymerization initiator at the following weight. Industrial Co., Ltd.), and stirred at 110 ° C for 2 hours under a stream of dry nitrogen. MMP 31.50 g glycidyl methacrylate 12.15 g diethylene glycol dimethacrylate 1.35 g V-601 2.03 g

The solution was cooled to room temperature to obtain a 30.0% by weight solution of the polymer (D) having an epoxy group. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (D) having an epoxy group was 4,000.

[Example 1] A 1000 ml separable flask equipped with a stirring wing was purged with nitrogen, and 40.00 g of the polyester ammonium acid (A) solution obtained in Synthesis Example 1 and 60.00 g of the M-402 as a compound having a polymerizable double bond, 0.06 g of 2-hydroxy-1,4-naphthoquinone as a molecular weight modifier, 1.2 g of NCI-930 as a photopolymerization initiator, and 12.00 g of having Epoxy polymer (D) solution, 1.2 g of EHPE3150 as an epoxy compound, 2.0 g of trimellitic anhydride (hereinafter abbreviated as "TMA") as an epoxy hardener, and 1.92 g of 3-glycidyl as an additive Polymer of oxypropyltrimethoxysilane (trade name: COATOSIL MP 200, Momentive Performance Materials contract company), 0.64 g of NT-200 (trade name; Toyo Synthetic Industry) Co., Ltd.), 0.06 g of ADK STAB AO-60 (trade name; ADEKA Co., Ltd.), 4.1 g of dehydrated and purified MMP, and 22.0 g of PGMEA, stirred for 3 hours at room temperature Dissolved uniformly. Next, 0.02 g of Megafac F-556 (trade name; DIC Corporation) was added, and the mixture was stirred at room temperature for 1 hour, and filtered with a membrane filter (0.2 μm) to prepare a photosensitivity.组合 物。 Composition.

[Example 2 to Example 4] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) shown in Table 1 to obtain a photosensitive composition.

Table 1

[Comparative Example 1 to Comparative Example 4] According to the method of Example 1, each component was mixed and dissolved at the ratio (unit: g) in Table 2 to obtain a photosensitive composition. Table 2

The obtained photosensitive composition was spin-coated on a glass substrate at 550 rpm for 10 seconds, and pre-baked on a hot plate at 100 ° C for 80 seconds. Next, exposure was performed in the air using a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.). The exposure amount was measured using a cumulative light meter UIT-102 (trade name; Ushio (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio (USHIO) Co., Ltd.) to measure 30 mJ / cm ² . The exposed coating film was developed with a buffer solution of sodium carbonate and sodium bicarbonate of 27 ° C for 40 seconds, and then the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. . Furthermore, it baked at 230 degreeC for 30 minutes, and obtained the glass substrate (1) with a cured film with a film thickness of 3.0 micrometers.

Except replacing the glass substrate with a glass substrate with ITO, according to the method for manufacturing a glass substrate with a cured film (1), a glass substrate with a cured film is obtained from each photosensitive composition (2 ).

The method described below was used to evaluate the residual film rate, adhesion, chemical resistance, heat resistance, and transparency after development using the glass substrate with a cured film (1). The glass with a cured film was used. The substrate (2) was evaluated for adhesion and chemical resistance.

[Evaluation method of residual film rate after development] The stepped, surface roughness, and fine shape measuring device (trade name: P-16, KLA TENCOR Corporation) was used to measure the glass substrate with a cured film. (1) The film thickness before development and the film thickness after development were calculated using the following calculation formulas. A case where the residual film rate after development was 80% or more was evaluated as ○, and a case where the residual film rate after development was less than 80% was evaluated as x. Residual film rate after development = (film thickness after development / film thickness before development) × 100

[Preparation of a substrate for analytical evaluation] Next, a photosensitive composition was spin-coated on a glass substrate at 550 rpm for 10 seconds, and pre-baked on a hot plate at 100 ° C for 80 seconds. Furthermore, in the air, a mask with holes and line patterns with a width of 30 μm was used to perform exposure using a proximity exposure machine TME-150PRC with an exposure gap of 100 μm. The exposure amount was measured using a cumulative light meter UIT-102 and a light receiver UVD-365PD, and was set to 30 mJ / cm ² . The exposed coating film was developed with a buffer solution of sodium carbonate and sodium bicarbonate of 27 ° C for 40 seconds, and then the coating film was washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C for 2 minutes. . Furthermore, it baked at 230 degreeC for 30 minutes in the oven, and obtained the glass substrate (3) with a cured film with a film thickness of 3.0 micrometers.

The cured film obtained in this manner was evaluated for analytical properties.

[Analytical evaluation method] The obtained glass substrate (3) with a pattern-shaped cured film was observed with a 1,000-fold optical microscope, and the analysis of holes and line patterns corresponding to the screen size of 30 μm was evaluated. Sex. The case where the hole and the line pattern were analyzed was evaluated as “○”, and the case where the hole and line patterns were not analyzed was evaluated as “×”.

[Evaluation method of heat resistance] After the obtained glass substrate (1) with a cured film was reheated at 230 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured and calculated from the following The formula calculates the residual film rate after heating and evaluates the heat resistance. The film thickness was measured using P-16. A case where the residual film rate after heating was 95% or more was evaluated as ○, and a case where the residual film rate after heating was less than 95% was evaluated as x. Residual film rate after heating = (film thickness after heating / film thickness before heating) × 100

[Evaluation method of transparency] In the obtained glass substrate (1) with a cured film, only a cured film was measured using an ultraviolet-visible near-infrared spectrophotometer (trade name: V-670, JASCO Corporation) The transmittance at 400 nm was evaluated, and the transparency was evaluated. A case where the transmittance was 95% or more was evaluated as ○, and a case where the transmittance was less than 95% was evaluated as ×.

[Evaluation method of adhesion] The adhesion was evaluated in accordance with JIS K 5600-5-6 (cross cutting test). That is, a tape peeling test was performed in which the obtained glass substrates (1) and (2) with a cured film were cut into 100 square grids of 1 mm × 1 mm, and cut into the grids. A cellophane tape (manufactured by 3M, Scotch (registered trademark) cellophane tape No. 610) was attached and peeled off. A case where the cured film in the grid was not peeled at all was evaluated as ○, a case where one third of the cured film in the box was peeled off was evaluated as △, and a case where one third or more was peeled off was evaluated as x.

[Evaluation method of chemical resistance] The obtained glass substrates (1) and (2) with a cured film were immersed in a 25 ° C ITO etching solution (trade name: ITO-301, manufactured by Kanto Chemical). After several minutes, wash with pure water and wipe off the water. Further, a tape peeling test was performed in which a cut was made to form 100 square squares of 1 mm × 1 mm, and a cellophane tape (manufactured by 3M, Scotch (registered trademark) cellophane tape was attached to the square. No. 610) and peeled off to evaluate chemical resistance. A case where the cured film in the grid was not peeled at all was evaluated as ○, a case where one third of the cured film in the box was peeled off was evaluated as △, and a case where one third or more was peeled off was evaluated as x.

Hereinafter, the evaluation results of the cured films of Examples 1 to 4 are described in Table 3, and the evaluation results of the cured films of Comparative Examples 1 to 4 are described in Table 4. table 3

Table 4

It is clear from the results shown in Table 3 that the cured film of Examples 1 to 4 has excellent residual film rate after development, resolution, heat resistance, transparency, adhesion, and chemical resistance. On the other hand, all of the evaluation items of the cured films of Comparative Examples 1 to 4 are not "○". As described above, in the case where a polyester sulfamic acid obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydroxy compound as essential raw materials is used, and the molecular weight of the epoxy compound is within the range of the present invention , Can meet all characteristics. [Industrial availability]

The cured film obtained from the photosensitive composition of the present invention has excellent properties as optical materials such as transparency, heat resistance, flatness, resolution, and chemical resistance, and can be used as a color filter in this respect. Sheets, protective films for various optical materials such as LED light emitting elements and light receiving elements, and transparent insulating films formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

no

Claims (16)

A photosensitive composition comprising: polyester amidate (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), a polymer (D) having an epoxy group, and a ring An oxygen compound (E), an epoxy hardener (F), and a molecular weight adjuster (G); the photosensitive composition is characterized in that the polyester amidate (A) Carboxylic dianhydride, Y Mole's diamine, and Z Mole's polyhydric hydroxy compound are obtained by reacting at a ratio where the relationship of the following formula (1) and formula (2) is established, and include the following formula (3) And a structural unit represented by the following formula (4); the compound (B) having a polymerizable double bond includes two or more polymerizable double bonds in each molecule; The weight average molecular weight of the polymer (D) is 3,000 to 50,000; the epoxy compound (E) contains 2 to 10 epoxy groups in each molecule, and the weight average molecular weight is less than 3,000; 100 parts by weight of ester amido acid (A), the total of the compound (B) having a polymerizable double bond 20 to 300 parts by weight, the total amount of the epoxy-containing polymer (D) and the epoxy compound (E) is 20 to 200 parts by weight; the photopolymerization initiator ( C) The content is more than 5.0 times and less than 30 times of the content of the molecular weight modifier (G); 0.2≤Z / Y≤8.0 ······ (1) 0.2≤ (Y + Z) / X≤5.0 ··· (2) In formulas (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is obtained by removing two -NH ₂ from a diamine. R ³ is a residue obtained by removing two -OH groups from a polyhydroxy compound. The photosensitive composition according to item 1 of the scope of patent application, wherein a raw material component of the polyester amidate further includes a monohydroxy compound. The photosensitive composition according to item 2 of the scope of patent application, wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl One or more of the methyl-3-hydroxymethyloxetane. The photosensitive composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the polyester amidine (A) is 1,000 to 200,000; the tetracarboxylic dianhydride Is selected from 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis ( 3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitic acid ester); The diamine is one or more selected from 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene; the polyhydroxy compound is selected from Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2- One or more of bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and tris (2-hydroxyethyl) isocyanurate; with respect to the polymerizable double bond The total weight of the compound, and the compound (B) having a polymerizable double bond contains at least 50% by weight selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol One or more of tetraacrylate, pentaerythritol triacrylate, ethylene isocyanate-modified triacrylate, and polyacid-modified (meth) acrylic acid oligomer; the photopolymerization initiator (C ) Is one or more selected from the group consisting of an α-amino benzoyl ketone system, a fluorenyl phosphine oxide system, and an oxime ester system photopolymerization initiator; the polymer (D) having an epoxy group is An epoxy-based copolymer of a reaction product of a mixture of a radically polymerizable monomer (d1) with an oxy group and a radically polymerizable monomer (d2) other than the (d1); and the epoxy hardener (F) is one or more kinds selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. The photosensitive composition according to item 4 of the scope of patent application, wherein the radically polymerizable monomer (d1) having an epoxy group is selected from glycidyl (meth) acrylate and (meth) acrylic acid 3 One or more of 4,4-epoxycyclohexyl methyl ester and 4-hydroxybutyl (meth) acrylate glycidyl ether; a radically polymerizable monomer (d2) other than (d1) containing a difunctional (meth) acrylic acid More than one kind of ester. The photosensitive composition according to any one of claims 1 to 5, in which the molecular weight modifier (G) is selected from the group consisting of thiols, xanthan acids, quinones, and hydroquinone One or more of 2,4-diphenyl-4-methyl-1-pentene. The photosensitive composition according to item 5 of the scope of patent application, wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2, One or more of 3,4-butanetetracarboxylic dianhydrides; the diamine is 3,3'-diaminodiphenylphosphonium; the polyhydroxy compound is 1,4-butanediol; the The monohydroxy compound is benzyl alcohol; The compound (B) having a polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyacid-modified (meth) acrylic acid oligomers. The difunctional (meth) acrylate is selected from ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylic acid Esters, 1,3-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, or more The total weight of the polymerization initiator (C), the photopolymerization initiator (C) contains more than 50% by weight selected from 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzylidene oxime), ethyl ketone, 1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy Group) one or more of phenylthio] phenyl] -2- (O-acetylamoxime); the epoxy hardener (F) is one or more selected from trimellitic anhydride and 2-undecylimidazole And the photosensitive composition further contains, as a solvent, one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate. The photosensitive composition according to any one of claims 1 to 7, wherein the molecular weight modifier (G) is one or more selected from naphthoquinones and hydroquinones. A cured film obtained from the photosensitive composition according to any one of claims 1 to 8 in the scope of patent application. A color filter has a hardened film as described in item 9 of the scope of patent application as a transparent protective film. A display element using the color filter described in item 10 of the scope of patent application. A solid-state imaging element using a color filter as described in claim 10 of the scope of patent application. A display element using a cured film as described in item 9 of the scope of the patent application as a transparent insulating film formed between a thin film transistor and a transparent electrode. A display element uses a cured film as described in item 9 of the scope of the patent application as a transparent insulating film formed between a thin film transistor and an alignment film. A light-emitting diode light-emitting body uses a cured film as described in item 9 of the scope of patent application as a protective film. An interlayer insulating film having a cured film as described in item 9 of the scope of patent application as a transparent protective film.