JP2018159920A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured film which dispenses with an organic solvent having high polarity, and is excellent in transparency, heat resistance, solvent resistance, adhesiveness, flatness and resolution, and a photosensitive composition providing the cured film, and to provide a cured film formed of the photosensitive resin composition, and an electronic component having the cured film.SOLUTION: A photosensitive composition contains a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound and an epoxy curing agent, where the polyester amide acid is obtained by reaction of a tetracarboxylic acid dianhydride, diamine and a polyvalent hydroxy compound as raw material components; and the compound having the polymerizable double bond contains a compound that contains two or more polymerizable double bonds in one molecule and has a molecular weight of less than 1,000, and a compound that has a polymerizable double bond and has a molecular weight of 1,000 or more.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive composition used for forming an insulating material in an electronic component, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a display element, or a protective film for a color filter. Related to things. Furthermore, it is related with the transparent film formed using the said photosensitive composition, and the electronic component which has the film | membrane.

  During the manufacturing process of elements such as display elements, various chemical treatments such as organic solvents, acids, alkali solutions, etc. are performed, and when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. There are things to do. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of various elements. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to an underlying substrate such as glass, transparency, scratch resistance, flatness, and light resistance are required. Is done. In addition, transparency, heat resistance, solvent resistance when used as a color filter protective film, as display elements have increased performance such as higher viewing angle, faster response, higher definition, and wider color gamut. Materials with improved properties and adhesion are desired.

  The types of curable compositions for forming these protective films can be broadly classified into photosensitive compositions and thermosetting compositions. Since the thermosetting composition is completely cured by high-temperature heating at the time of film formation, even if it is heated to a high temperature in the subsequent steps, the generated volatile matter is small and excellent in heat resistance. As a thermosetting protective film material having such excellent characteristics, there is a polyester amide acid composition (see, for example, Patent Document 1). However, the thermosetting composition cannot form a scribe line, and a large amount of fine debris of the protective film is generated when the manufacturing panel is divided, so that an advanced panel cleaning process is required thereafter. .

  On the other hand, the photosensitive composition comprises a polymer, oligomer or monomer having a photopolymerizable group and a photopolymerization initiator, and causes a chemical reaction by the energy of light such as ultraviolet rays to be cured. For example, the photosensitive composition can easily form a scribe line to be used when dividing the production panel, and thus there is an advantage that fine debris of the protective film is not generated. On the other hand, the protective composition formed by the ordinary photosensitive composition is used. The film has insufficient heat resistance as compared with a protective film formed by the thermosetting composition.

  In recent years, the need for a protective film that requires heat resistance and solvent resistance has increased, and the need for a protective film that requires a fine pattern shape has also increased. Accordingly, there is a demand for a photosensitive composition that can form a protective film excellent in heat resistance and solvent resistance and that can form a fine pattern.

  As a photosensitive composition which can form the protective film which has the very outstanding heat resistance, a polyimide precursor composition (for example, refer patent document 2) and a soluble polyimide composition (for example, refer patent document 3). There is. However, in any photosensitive composition, the organic solvent capable of dissolving the obtained polyimide precursor composition or soluble polyimide composition is limited, and an organic solvent having a very high polarity is required.

  Examples of the highly polar organic solvent in which the polyimide precursor composition, the soluble polyimide composition and the like are dissolved include pyrrolidone, sulfoxide, formamide, acetamide, phenol, tetrahydrofuran, dioxane, γ-butyrolactone, and the like.

  In particular, when these photosensitive compositions are used as a color filter protective film, if these highly polar organic solvents are contained, the underlying color filter layer is eroded, and for example, coloring materials such as pigments or dyes contained in pixels are formed. Since it elutes, it becomes difficult to produce a high-quality display element.

  As an example of using the photosensitive composition for the protective film of the color filter, there is Patent Document 4, but using the photosensitive composition described therein, the present inventors form a protective film and adhere to the film. As a result of confirming the property, the adhesion is not sufficiently satisfied, and further improvement is desired.

  Moreover, it is requested | required that these curable compositions are excellent in the applicability | paintability to a base substrate irrespective of a photosensitive composition and a thermosetting composition.

JP2008-156546A JP 59-068332 A JP2002-003516 JP2011-090275A

  The problem of the present invention is that a highly polar organic solvent is not required, and in particular, a cured film excellent in transparency, heat resistance, solvent resistance, adhesion, flatness, and resolution, and photosensitivity that provides this cured film It is to provide a composition. It is to provide a cured film formed by the photosensitive composition, and further to provide an electronic component having the cured film.

As a result of intensive studies to solve the above problems, the present inventors have found that one molecule of polyester amic acid obtained from the reaction of a compound containing tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, and a polymerizable double bond. A compound having a molecular weight of less than 1,000 containing 2 or more per unit, a compound having a polymerizable double bond having a molecular weight of 1,000 or more, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent, and the composition It has been found that the above object can be achieved by a cured film obtained by curing, and the present invention has been completed.
The present invention includes the following configurations.

式（３）及び式（４）において、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基である。 [1] A photosensitive composition comprising a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent;
The polyester amic acid is reacted with X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied. And having a structural unit represented by the following formula (3) and a structural unit represented by the formula (4);
The compound having a polymerizable double bond includes a compound having a molecular weight of less than 1,000 having two or more polymerizable double bonds per molecule, and a compound having a molecular weight of 1,000 or more having a polymerizable double bond,
The weight of the compound having a molecular weight of 1,000 or more having a polymerizable double bond is 1 to 50% by weight based on the total weight of the compound having a polymerizable double bond;
The total amount of the compound having a polymerizable double bond is 20 to 300 parts by weight, the total amount of the epoxy compound is 20 to 200 parts by weight, and the total amount of the photopolymerization initiator is 100 parts by weight of the polyester amic acid. 1 to 60 parts by weight of a photosensitive composition;

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.

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

[3] The monohydroxy compound is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. ] The photosensitive composition of a term.

[4] The photosensitive composition according to any one of [1] to [3], wherein the polyester amic acid has a weight average molecular weight of 1,000 to 200,000.

[5] The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2 , 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) One or more selected;
The diamine is one or more selected from 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;
The polyvalent hydroxy compound is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, One or more selected from 2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl and tris (2-hydroxyethyl) isocyanurate;
Compounds having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule are dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified tri Containing at least 50% by weight of at least one selected from acrylates and polybasic acid-modified (meth) acrylic oligomers with respect to the total weight of the compound having a molecular weight of less than 1,000 containing two or more polymerizable double bonds per molecule And
The compound having a polymerizable double bond and a molecular weight of 1,000 or more is a macromonomer;
The photopolymerization initiator is one or more selected from α-aminoalkylphenone series, acylphosphine oxide series, and oxime ester series photopolymerization initiators;
And the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole,
[1] The photosensitive composition according to any one of [4].

[6] One kind in which the tetracarboxylic dianhydride is selected from 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Or more;
The diamine is 3,3′-diaminodiphenylsulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
The monohydroxy compound is benzyl alcohol;
One or more compounds selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified (meth) acrylic oligomer, wherein the compound having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule Is;
The compound having a polymerizable double bond and a molecular weight of 1,000 or more is a methacryloylated polymethyl methacrylate oligomer;
The photopolymerization initiator is 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- One or more selected from (O-acetyloxime) is contained in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator;
The epoxy curing agent is one or more selected from trimellitic anhydride and 2-undecylimidazole; and
The photosensitive composition according to any one of [2] to [5], further containing at least one selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.

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

[8] A color filter using the cured film according to the item [7] as a protective film.

[9] A display device using the color filter according to the item [8].

[10] A solid-state imaging device using the color filter according to the item [8].

[11] A display device using the cured film according to the item [7] as a transparent insulating film formed between the TFT and the transparent electrode.

[12] A display device using the cured film according to the item [7] as a transparent insulating film formed between the transparent electrode and the alignment film.

[13] An LED luminous body using the cured film according to the item [7] as a protective film.

  The photosensitive composition according to a preferred embodiment of the present invention is a material that does not require a highly polar organic solvent and can form a cured film that is particularly excellent in transparency, heat resistance, adhesion, flatness, and resolution. In addition, when used as a color filter protective film of a color display element, display quality and reliability can be improved. From the above, it is very practical and is particularly useful as a protective film for a color filter produced by a dyeing method, a pigment dispersion method, an electrodeposition method and a printing method. It can also be used as a protective film and a transparent insulating film for various optical materials.

1. Photosensitive Composition The photosensitive composition of the present invention is a composition comprising a polyester amide acid, a compound containing a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent. The polyester amic acid can be obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components. The component ratio of the photosensitive composition of the present invention is such that the compound having a polymerizable double bond is 20 to 300 parts by weight, the epoxy compound is 20 to 200 parts by weight, and photopolymerization is started with respect to 100 parts by weight of the polyester amide acid. The agent is 1 to 60 parts by weight. In addition, the compound having a polymerizable double bond includes a compound having a molecular weight of less than 1,000 containing two or more polymerizable double bonds per molecule, and a compound having a molecular weight of 1,000 or more having a polymerizable double bond, Further, the weight of the compound having a polymerizable double bond and having a molecular weight of 1,000 or more is 1 to 50% by weight based on the total weight of the compound having a polymerizable double bond. In addition, the photosensitive composition of this invention may further contain other components other than the above in the range in which the effect of this invention is acquired.

1-1. Polyester amide acid The polyester amide acid of this invention is obtained by making tetracarboxylic dianhydride, diamine, and a polyvalent hydroxy compound react as an essential raw material component. More specifically, X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compound are reacted at a ratio such that the relationship of the following formulas (1) and (2) is established. Is obtained.

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

式（３）及び式（４）において、Ｒ^１はテトラカルボン酸二無水物から２つの−ＣＯ−Ｏ−ＣＯ−を除いた残基であり、好ましくは炭素数２〜３０の有機基である。Ｒ^２はジアミンから２つの−ＮＨ_２を除いた残基であり、好ましくは炭素数２〜３０の有機基である。Ｒ^３は多価ヒドロキシ化合物から２つの−ＯＨを除いた残基であり、好ましくは炭素数２〜２０の有機基である。 The polyester amide acid of this invention has a structural unit represented by following formula (3), and a structural unit represented by Formula (4).

In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, 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 from a polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

  The synthesis of the polyester amide acid of the present invention requires at least a solvent. The solvent may be left as it is to form a liquid or gel photosensitive composition in consideration of handling properties, etc., or the solvent may be removed. It is good also as a solid composition in consideration of transportability. In addition, the synthesis of the polyester amide acid may contain, as necessary, one or more compounds selected from a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material. It preferably contains a hydroxy compound. In addition, the synthesis of the polyester amic acid may contain other compounds than the above as a raw material as necessary, as long as the object of the present invention is not impaired. Examples of such other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining a polyester amide acid. Specific examples of preferred tetracarboxylic dianhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2, 3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylsulfonetetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Diphenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1 2,3,4-butanetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate) (trade name; TMEG-100, Shin Nippon Rika Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetra Mention may be made of carboxylic dianhydrides, cyclopentanetetracarboxylic dianhydrides, cyclohexanetetracarboxylic dianhydrides, and ethanetetracarboxylic dianhydrides. One or more of these can be used.

  Among these, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride give good transparency to the cured film. 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and TMEG-100 are more preferable, 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride Is particularly preferred.

1-1-2. Diamine In the present invention, diamine is used as a material for obtaining the polyester amide acid. Specific examples of preferred diamines include 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone, Mention may be made of [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] sulfone and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. One or more of these can be used.

  Among these, 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone that give good transparency to the cured film are more preferable, and 3,3′-diaminodiphenylsulfone is particularly preferable. preferable.

1-1-3. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as a material for obtaining a polyester amide acid. Specific examples of preferable polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, weight Polypropylene glycol having an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2,4-pentane Diol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1, 7 Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, 1,2-nonanediol, 1 , 9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecane Diol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, isocyanuric acid tris (2-hydroxyethyl), bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxy Phenyl) sulfone), bisphenol F (bis (4-hydro) Shifeniru) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxy dicyclohexyl, diethanolamine, and it can be given triethanolamine. One or more of these can be used.

  Among these, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl, and tris (2-hydroxyethyl) isocyanurate are more preferable, 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 may be used as a material for obtaining polyester amide acid. By using a monohydroxy compound, the storage stability of the photosensitive composition is 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, diethylene glycol monoethyl. Mention may be made of ether, diethylene glycol monomethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyloxetane and dimethylbenzyl carbinol. One or more of these can be used.

  Among these, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable. In consideration of compatibility when a polyester amide acid formed using these, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent are mixed, and applicability on a color filter of a photosensitive composition, a monohydroxy compound Particularly preferred is the use of benzyl alcohol.

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

1-1-5. Styrene-maleic anhydride copolymer The polyesteramic acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above raw material. By doing so, since the transparency of a cured film improves, it is preferable. Examples of the compound having 3 or more acid anhydride groups include a styrene-maleic anhydride copolymer. About the ratio of each component which comprises a styrene-maleic anhydride copolymer, the molar ratio of styrene / maleic anhydride is 0.5-4, Preferably it is 1-3. Furthermore, 1 or 2 is more preferable, and 1 is particularly preferable.

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

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

1-1-6. In the synthesis of silicon-containing monoamine polyester amic acid, as a raw material, other raw materials other than the above may be included as necessary, as long as the purpose of the present invention is not impaired. And silicon-containing monoamines.

  Specific examples of preferable silicon-containing monoamines used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 4-amino. Butyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Mention may be made of methyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these can be used.

  Among these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane that improve the acid resistance of the cured film are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable from the viewpoint of acid resistance and compatibility. preferable.

  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 polyvalent hydroxy compound. More preferably, it is 5-200 weight part.

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

1-1-8. Polyester amide acid synthesis method In the polyester amide acid synthesis method used in the present invention, tetracarboxylic dianhydride X mole, diamine Y mole, and polyhydric hydroxy compound Z mole are reacted in the solvent. At this time, it is preferable that X, Y, and Z are set to such a ratio that the relationship of the following formulas (1) and (2) is established between them. Within this range, the solubility of the polyester amide acid in the solvent is high, so that the coating property of the composition is improved, and 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 the formula (1), preferably 0.7 ≦ Z / Y ≦ 7.0, and more preferably 1.0 ≦ Z / Y ≦ 5.0. In the formula (2), preferably 0.5 ≦ (Y + Z) /X≦4.0, and more preferably 0.6 ≦ (Y + Z) /X≦2.0.

  In the polyester amic acid used in the present invention, the molecule having an acid anhydride group (—CO—O—CO—) at the terminal is formed at the terminal under the condition where X is excessively used relative to Y + Z in the above reaction conditions. It is thought that it is produced in excess of molecules having amino groups or hydroxyl groups. In the case of reacting in such a monomer structure, the monohydroxy compound described above can be added, if necessary, in order to react with the acid anhydride group at the molecular terminal to esterify the terminal. Polyester amide acid obtained by adding and reacting a monohydroxy compound has improved compatibility with an epoxy compound and an epoxy curing agent, and also improved applicability of the photosensitive composition of the present invention containing them. Is done.

  Moreover, when making it react with the structure of the monomer mentioned above, in order to make it react with the acid anhydride group of a molecular terminal and introduce | transduce a silyl group at the terminal, a silicon-containing monoamine can be added. When the photosensitive composition of the present invention containing the polyester amide acid obtained by adding and reacting with a silicon-containing monoamine is used, the acid resistance of the resulting cured film is improved. Furthermore, when making it react by the structure of the monomer mentioned above, both a monohydroxy compound and a silicon-containing monoamine can also be added and made to react.

  The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound, since the reaction proceeds smoothly. The reaction is preferably carried out at 40 to 200 ° C. for 0.2 to 20 hours.

  The order of adding the reaction raw materials to the reaction system is not particularly limited. That is, a tetracarboxylic dianhydride, a diamine and a polyvalent hydroxy compound are simultaneously added to the reaction solvent. After the diamine and the polyvalent hydroxy compound are dissolved in the reaction solvent, the tetracarboxylic dianhydride is added. After reacting acid dianhydride and polyvalent hydroxy compound in advance, diamine is added to the reaction product, or after reacting tetracarboxylic dianhydride and diamine in advance, polyhydric hydroxy is added to the reaction product. Any method such as adding a compound can be used.

  In the case of reacting the silicon-containing monoamine, after the reaction of the tetracarboxylic dianhydride, the diamine and the polyvalent hydroxy compound is completed, the reaction liquid is cooled to 40 ° C. or lower, and then the silicon-containing monoamine is added. It is good to make it react at 10-40 degreeC for 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

  The polyester amide acid synthesized in this way contains the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and the terminal thereof is a tetracarboxylic dianhydride or diamine as a raw material. Alternatively, it is an acid anhydride group, amino group or hydroxy group derived from a polyvalent hydroxy compound, or an additive other than these compounds constitutes the terminal. By including such a configuration, curability is improved.

  The resulting polyester amic acid preferably has a weight average molecular weight of 1,000 to 200,000, 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 the present specification is a value in terms of polystyrene determined by GPC method (column temperature: 35 ° C., flow rate: 1 ml / min). Standard polystyrene has a molecular weight of 645-132,900 (for example, polystyrene calibration kit PL2010-0102 from Agilent Technologies), and PLgel MIXED-D (Agilent Technology) is used for the column. It can be measured using THF as the phase. In addition, the weight average molecular weight of the commercial item in this specification is a catalog publication value.

1-2. Compound having a polymerizable double bond 1-2-1. A compound having a molecular weight of less than 1,000 containing two or more polymerizable double bonds per molecule. A compound having a molecular weight of less than 1,000 containing two or more polymerizable double bonds used in the present invention satisfies this requirement. If it is a compound, it will not specifically limit. The compound having a polymerizable double bond is preferably 20 to 300 parts by weight with respect to 100 parts by weight of the polyester amide acid because the residual film ratio after development is good.

  Examples of the compound having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule contained in the photosensitive composition of the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydrin modified diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (Meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (Meth) acrylate, epichlorohydrin modified dipropylene glycol di (meth) acrylate, epichlorohydrin modified tripropylene glycol di (meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide modified trimethylo Propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate , Glycerol tri (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, methoxylated cyclohexyldi (meth) Acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate Rate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide modified acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified penta Erythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol tetra (meth) acrylate, alkyl-modified dipentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (me ) Acrylate, polybasic acid modified (meth) acryl oligomer, allylated cyclohexyl di (meth) acrylate, bis [(meth) acryloxyneopentyl glycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) ) Acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate 1,3-butylene glycol (meth) acrylate, dicyclopentanyl diacrylate, polyester diacrylate, polyester triacrylate, polyester polyester Laacrylate, polyester pentaacrylate, polyester hexaacrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate Epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric Acid ethylene oxide modified triacrylate, caprolactone modified tris [(meth) acryloxyethyl] isocyanate Nurate, (meth) acrylated isocyanurate, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer Examples thereof include a polymer, pentaerythritol triacrylate, isophorone diisocyanate, urethane prepolymer, and the like.

  As the compound having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule, the above-mentioned compounds may be used alone, or two or more may be used in combination.

  Among compounds having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , Polybasic acid-modified (meth) acryl oligomer, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, epoxy acrylate oligomer or a mixture thereof is preferable from the viewpoint of heat resistance and solvent resistance of the cured film. .

  Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modified (meth) acryl oligomer, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified tri As the acrylate, epoxy acrylate oligomer or a mixture thereof, the following commercially available products can be used. A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; Toagosei Co., Ltd.). Specific examples of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronics M-306 (65-70 wt%), M-305 (55-63 wt%), and M-450 (less than 10 wt%) ( All are brand names; Toagosei Co., Ltd., and the content in parentheses is the catalog content of the content of pentaerythritol triacrylate in the mixture). Specific examples of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronics M-403 (50-60 wt%), M-400 (40-50 wt%), M-402 (30-40 wt%). ), M-404 (30-40% by weight), M-406 (25-35% by weight), and M-405 (10-20% by weight) (all trade names: Toagosei Co., Ltd., contained in parentheses) The rate is the catalog listed value of the content of dipentaerythritol pentaacrylate in the mixture. Specific examples of the polybasic acid-modified (meth) acryl oligomer are Aronix M-510 and M-520 (both are trade names; Toagosei Co., Ltd.). A specific example of the isocyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name; Toagosei Co., Ltd.). A specific example of a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate is Aronix M-315 (3 to 13% by weight) (trade name; Toagosei Co., Ltd., the content in parenthesis is isocyanuric in the mixture Catalog value of the content of acid ethylene oxide-modified diacrylate). A specific example of the epoxy acrylate oligomer is TEA-100 (trade name; KSM Corporation).

1-2-2. Compound having a molecular weight of 1,000 or more having a polymerizable double bond The photosensitive composition of the present invention preferably contains a compound having a molecular weight of 1,000 or more having a polymerizable double bond from the viewpoint of adhesion. The content of the compound having a polymerizable double bond and a molecular weight of 1,000 or more is preferably 1 to 50% by weight, and preferably 1 to 30% by weight, based on the total weight of the compound having a polymerizable double bond. It is more preferable from the viewpoint of resolution.

  The compound having a polymerizable double bond contained in the photosensitive composition of the present invention and having a molecular weight of 1,000 or more includes dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, non-yellowing type oligourethane acrylate, carboxylic acid Examples thereof include urethane acrylate oligomers, epoxy acrylate oligomers, and macromonomers. The macromonomer has a polymerizable carbon-carbon unsaturated double bond at the end of the molecular chain, and is a reactive oligomer or polymer having a number average molecular weight of usually 1,000 to 30,000.

  As such a macromonomer available as a commercial product, one-terminal methacryloylated polymethyl methacrylate oligomer (Mn = 6,000, trade name: AA-6, manufactured by Toagosei Co., Ltd.) and one-terminal methacryloylated poly-n -Butyl acrylate oligomer (Mn = 6,000, trade name: AB-6, manufactured by Toagosei Co., Ltd.), one-end methacryloylated polystyrene oligomer (Mn = 6,000, trade name; AS-6, Toagosei Co., Ltd.) ) Made).

  As the compound having a polymerizable double bond and having a molecular weight of 1,000 or more, the above compounds may be used alone, or two or more may be used in combination.

1-2-3. Compound having one polymerizable double bond per molecule and having at least one functional group selected from —OH and —COOH per molecule From the viewpoint of resolution in the photosensitive composition of the present invention And a compound having one polymerizable double bond per molecule and having at least one functional group selected from —OH and —COOH per molecule. The compound having one polymerizable double bond per molecule and having at least one functional group selected from —OH and —COOH per molecule is 1 to 50 weights per 100 weight parts of polyester amic acid. It is preferable that it is a part because the resolution is good.

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

  Among these, phthalic acid 2- (meth) acryloyloxyethyl, (meth) acrylic acid 4-hydroxyphenyl and p-hydroxy (meth) acrylanilide are preferable because of good resolution.

1-3. Photopolymerization initiator The photopolymerization initiator contained in the photosensitive composition of the present invention is a composition containing polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent. The polymerization is not particularly limited as long as the polymerization can be initiated.

Examples of the photopolymerization initiator contained in the photosensitive composition of the present invention include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, and 2-ethyl. Anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4′-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2- Diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 ON (eg, trade name: IRGACURE 907, BASF Japan Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (eg, trade name: IRGACURE 369, BASF Japan Ltd.) ), Ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (for example, trade name: IRGACURE OXE01, BASF Japan Ltd.), ethanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazo -3-yl]-, 1- (O-acetyloxime) (for example, trade name; IRGACURE OXE02, BASF Japan Ltd.), OXE03 (trade name; BASF Japan Ltd.), OXE04 (trade name; BASF Japan Ltd.) ), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) (eg, trade name; Adeka Arcles NCI-930, shares ADEKA), Adeka Arcles NCI-831 (trade name; ADEKA Corporation), Adekaoptomer N-1919 (trade name; ADEKA Corporation), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- ( 4'-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (3 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ′, 4′-dimethoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2 '-Chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 3- (2 Methyl-2-dimethylamino-propionyl) carbazole, 3,6-bis (2-methyl-2-morpholino-propionyl) -9-n-dodecyl carbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (eta ^5-2,4- And cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.

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

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

1-4. Epoxy compound The epoxy compound used for this invention will not be specifically limited if it is a compound containing an epoxy group. The epoxy compound is preferably 20 to 150 parts by weight with respect to the polyester amide acid because of good flatness.

  Preferred examples of the epoxy compound include 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celoxide 2021P, Daicel Corporation), 1-methyl-4- (2-methyl Oxiranyl) -7-oxabicyclo [4.1.0] heptane (for example, trade name: Celoxide 3000, Daicel Corporation), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [ 4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] ] -1- [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy]- A mixture with -propanol (for example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethanetriglycidyl ether (for example, trade name: jER 1032H60, Mitsubishi Chemical Corporation), 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2-bis (hydroxymethyl) 1,2-Epoxy-4- (2-oxiranyl) cyclohexane adduct of -1-butanol (for example, trade name: EHPE3150, stock) Company Daicel), and epoxy group-containing copolymer.

  The epoxy group-containing copolymer can be obtained by reacting glycidyl (meth) acrylate with another radical polymerizable monomer. Use of an epoxy group-containing copolymer is preferable because transparency of a cured film obtained from the photosensitive composition is increased, and a decrease in transparency in a UV ozone treatment step or an ultraviolet exposure step can be suppressed. It is preferable from a viewpoint of flatness and heat resistance that glycidyl (meth) acrylate accounts for 50 to 99 weight% in all the monomers which comprise an epoxy-group-containing copolymer.

  Examples of other radical polymerizable monomers include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or higher polyfunctional (meth) acrylate. In order to improve the heat resistance and solvent resistance of the cured film obtained from the photosensitive composition, it is preferable to use a trifunctional or higher polyfunctional (meth) acrylate, while the flatness of the cured film, in the composition Monofunctional (meth) acrylate is preferably used in order to improve the compatibility with the polyester amide acid. However, the heat resistance of the cured film, the solvent resistance and the flatness of the cured film, and the compatibility with the polyester amide acid in the composition tend to trade off. It is preferable to use a bifunctional (meth) acrylate.

  Preferred examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-butanediol di (meth) acrylate. , Neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. These are preferable because the compatibility of the epoxy group-containing copolymer obtained by reacting with glycidyl (meth) acrylate with the polyester amide acid is improved. The bifunctional (meth) acrylate is preferably contained in an amount of 1 to 30% by weight in all monomers constituting the epoxy group-containing copolymer from the viewpoint of flatness and heat resistance.

  The epoxy compound may contain a radical polymerizable monomer other than glycidyl (meth) acrylate and bifunctional (meth) acrylate as a raw material component. Such other radical polymerizable monomers are preferably contained in an amount of 0 to 20% by weight from the viewpoint of developing the characteristics of the other radical polymerizable monomers without impairing the effects of the present invention. 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 monofunctional (meth) acrylates are methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) Acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Glycerol mono (meth) acrylate, m-phenoxybenzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.

  Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropane ethoxytriacrylate, trimethylolpropane propoxytriacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, glycerin ethoxytriacrylate, glycerin propoxytriacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate.

  The weight average molecular weight of the epoxy group-containing copolymer obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components is preferably 3,000 to 50,000, 000 to 20,000 is more preferable. If the molecular weight is within these ranges, sufficient resolution, flatness, and heat resistance can be obtained.

  Further, for example, a silane compound having an epoxy group, such as a polymer of 3-glycidyloxypropyltrimethoxysilane, which is known as a trade name COATOSIL MP 200 (Momentive Performance Materials Japan GK) is also suitable. Can be used for Since such a compound has an alkoxysilyl group in the molecule, an effect of improving the adhesion between the cured film to be formed and the substrate is expected as a “coupling agent” described later.

1-5. Epoxy curing agent An epoxy curing agent is used in the photosensitive composition of the present invention in order to improve flatness, heat resistance, and solvent resistance. Epoxy curing agents include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalytic curing agents, and sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, and the like. Although there exist a heat-sensitive acid generator etc., an acid anhydride type hardening | curing agent or an imidazole type hardening | curing agent is preferable from a viewpoint of avoiding coloring of a cured film and the heat resistance of a cured film.

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

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

1-6. Ratio of polyester amic acid, compound having a polymerizable double bond, photopolymerization initiator, epoxy compound, and epoxy curing agent In the photosensitive composition of the present invention, a polymerizable double bond is added to 100 parts by weight of polyester amic acid. The ratio of the compound to have is 20-300 weight part. When the ratio of the compound having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance and remaining film ratio after development is good. More preferably, the compound having a polymerizable double bond is in the range of 50 to 200 parts by weight.

  The ratio of the photopolymerization initiator with respect to 100 parts by weight of the polyester amic acid is 1 to 60 parts by weight. It is preferable from the viewpoint of the sensitivity of the coating film during exposure that the ratio of the photopolymerization initiator is within this range. The photopolymerization initiator is 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) or 1,2-propanedione, 1- [4- [4- When (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is 20% by weight or more based on the total weight of the photopolymerization initiator, the sensitivity of the coating film at the time of exposure and the transparency of the cured film From the viewpoint of Moreover, it is further more preferable in it being 50 weight% or more.

  In the photosensitive composition of the present invention, the ratio of the epoxy compound to 100 parts by weight of the polyester amide acid is 20 to 200 parts by weight. When the proportion of the epoxy compound is within this range, the balance between heat resistance and flatness is good. The epoxy compound is more preferably in the range of 20 to 150 parts by weight.

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

1-7. Other Components Various additives can be added to the photosensitive composition of the present invention in order to improve resolution, coating uniformity, and adhesiveness. Additives include solvents, molecular weight modifiers, photoacid generators, anionic, cationic, nonionic, fluorine or silicon surfactants, coupling agents such as silane coupling agents, hindered phenols, Mainly mentioned are antioxidants such as hindered amine, phosphorus and sulfur compounds.

1-7-1. Solvent A solvent may be added to the photosensitive composition of the present invention. The solvent optionally added to the photosensitive composition of the present invention is preferably a solvent capable of dissolving polyester amic acid, a compound having a polymerizable double bond, an epoxy compound, an epoxy curing agent and the like. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2 -Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl loxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate Methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene Recall monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether,. One of these may be sufficient as a solvent, and these 2 or more types of mixtures may be sufficient as it.

1-7-2. Molecular Weight Modifier A molecular weight modifier may be added to the photosensitive composition of the present invention in order to suppress an increase in molecular weight due to polymerization and to exhibit excellent resolution. Examples of the molecular weight modifier include mercaptans, xanthogens, quinones, hydroquinones, phenols, catechols, cresols, 2,4-diphenyl-4-methyl-1-pentene, phenothiazine and the like.

  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, anthraquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzonorbornane, 4-methoxyphenol, 2,2 ', 6,6'-tetra-t-butyl-4,4'-dihydroxybiphenyl, stearyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylenebis ( 6-t-butyl-4-ethylphenol), 2,4,6-tris (3 ′, 5′-di-t-butyl- '-Hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4-t-butylpyrocatechol, n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethylxanthogen sulfide, diisopropylxanthogen disulfide, 2,6-di-t-butyl-p-cresol, 4,4'-butylidenebis (6-t-butyl-m -Cresol), 4,4'-thiobis (6-t-butyl-m-cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine.

1-7-3. 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 1,2-quinonediazide compounds include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide. -5-sulfonic acid ester (for example, trade name: NT-200, Toyo Gosei Chemical Industry), 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6 -Trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, bis (p-hydroxyphenyl) meta -1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester; tri (p-hydroxyphenyl) methane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester; bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-tri Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2 , 2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl)- 3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] fur Nyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol -1,2-naphthoquinonediazide-5-sulfonic acid ester; bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2 , 5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobi Indene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-s Phosphonate ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide— 5-sulfonic acid ester; 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, and 2,2,4-trimethyl-7, 2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester.

1-7-4. Surfactant A surfactant may be added to the photosensitive composition of the present invention in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 75, Polyflow No. 90, polyflow no. 95 (all trade names: Kyoeisha Chemical Co., Ltd.), Disperbeek 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181 and Disper Bake 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all trade names; BYK Chemie Japan KK), KP-341, KP-368, KF-96- 50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade names; AGC Seimi Chemical Co., Ltd.), Agent 222F, Agent 208G, Agent 251, Agent 710FL, Agent 710FM, Agent 710FS, Agent 601AD, Agent 650A, FTX-218 (all trade names; Neos Inc.), Megafuck F-410 , Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck F-556, Mega Fuck F-558, Mega Fuck F-559, Mega Fuck R-94, Mega Fuck RS-75, Mega Fuck RS-72-K, Mega Fuck RS-76-NS , Gafac DS-21 (all trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names; Evonik Japan Co., Ltd.), Fluoroalkylbenzene sulfonate, Fluoroalkyl carboxylate, Fluoroalkyl polyoxyethylene ether, Fluoroalkyl ammonium iodide, Fluoroalkyl betaine, Fluoroalkyl sulfonate, Diglycerin tetrakis (Fluoroalkyl polyoxyethylene ether), Fluoroalkyltrimethyl Ammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, poly Xylethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, poly Oxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate , Polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, poly Examples include reoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferable to use at least one selected from these.

  Among these surfactants, BYK306, BYK342, BYK346, KP-341, KP-368, Surflon S611, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, Megafuck F-477 , Megafuck F-556, Megafuck F-559, Megafuck RS-72-K, Megafuck DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate, Fluoroalkylcarboxylate, Fluoroalkylpolyoxyethylene ether, Photosensitivity when at least one selected from fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amino sulfonate This is preferable because the coating uniformity of the composition is increased.

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

1-7-5. Coupling Agent The photosensitive composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the formed cured film and the substrate.

  As such a coupling agent, for example, a silane, aluminum, or titanate coupling agent can be used. Specifically, 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Silaace S510, JNC Corporation), 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Silaace S530, JNC Corporation), 3-mercaptopropyltrimethoxysilane (for example, trade name: Silaace S810, JNC Corporation), etc. Agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate, and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate. In addition, although it is COATOSIL MP200 mentioned above as an epoxy compound, it can use similarly to the said coupling agent under the classification | category with the silane coupling agent which has an epoxy group.

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

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

1-7-6. 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.

  You may add antioxidants, such as a hindered phenol type | system | group, a hindered amine type | system | group, a phosphorus type | system | group, and a sulfur type compound, to the photosensitive composition of this invention. Of these, hindered phenols are preferred from the viewpoint of weather resistance. As a specific example, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox259, Irganox3114, Irganox565, (all trade name; BASF Japan Co., Ltd. ), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all trade names; ADEKA Corporation) Can be mentioned. Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

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

1-8. Storage of Photosensitive Composition When the photosensitive composition of the present invention is stored in the range of −30 ° C. to 25 ° C., the composition is preferably stable over time. If the storage temperature is −20 ° C. to 10 ° C., there is no precipitate and it is more preferable.

2. Cured Film Obtained from Photosensitive Composition The photosensitive composition of the present invention comprises a polyester amic acid, a compound having a polymerizable double bond, an epoxy compound, an epoxy curing agent, and a molecular weight modifier. Further, a solvent, a coupling agent, a surfactant, and other additives can be selected and added as necessary, and they can be mixed and dissolved uniformly.

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

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

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

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

  The cured film thus obtained is further heated at the time of 1) the polyamic acid portion of the polyester amic acid is dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amic acid reacts with the epoxy group-containing polymer. Therefore, it is very tough and excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state image sensor can be produced using this color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. It is. Furthermore, the cured film of the present invention is effective even when used as a protective film for LED light emitters.

  Next, although a synthesis example, a reference example, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples. As for the abbreviations of the compounds in Tables 1 and 2, M-520 is a compound having a polymerizable double bond, Aronix M-520 (trade name; Toagosei Co., Ltd.), and AA-6 has a polymerizable double bond. Compound AA-6 (trade name; Toagosei Co., Ltd.), NCI-930 is a photopolymerization initiator Adeka Arcles NCI-930 (trade name; ADEKA Co., Ltd.), EHPE3150 is an epoxy compound EHPE3150 (trade name; Daicel Corporation) ), VG3101L is an epoxy compound TECHMORE VG3101L (trade name; Printtech Co., Ltd.), TMA is an epoxy curing agent trimellitic anhydride, S510 is a coupling agent, Sailer Ace S510 (trade name; JNC Corporation), and AO-60 is oxidized. Inhibitor ADK STAB AO-60 (trade name; ADEKA), F-556 is a surfactant, MegaFac F-556 (trade name; DIC Corporation), MMP is a solvent 3-methoxypropionate, EDM is a solvent, diethylene glycol ethyl methyl ether, PGMEA is a solvent, propylene glycol monomethyl ether acetate MBA is a solvent, 3-methoxybutyl acetate.

  First, a polyester amic acid solution composed of reaction products such as tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound was synthesized as shown below (Synthesis Example 1).

[Synthesis Example 1] Synthesis of polyester amic acid (A) solution In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, diethylene glycol ethyl methyl ether (hereinafter abbreviated as “EDM”), 4,4′-diphenyl ether tetracarboxylic acid A dianhydride (hereinafter abbreviated as “ODPA”), SMA1000P, 1,4-butanediol, and benzyl alcohol were charged in the order of the following weights, followed by stirring at 120 ° C. for 3 hours in a dry nitrogen stream.
PGMEA 504.00g
EDM 96.32g
ODPA 47.70g
SMA1000P 144.97g
1,4-butanediol 9.23 g
Benzyl alcohol 55.40 g

Thereafter, the reaction solution was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as DDS) and EDM were added in the following weights, stirred at 20-30 ° C. for 2 hours, and then at 120 ° C. Stir for 2 hours.
DDS 12.72g
EDM 29.68g

[Z / Y = 2.0, (Y + Z) /X=1.0]

  The solution was cooled to room temperature to obtain a 30% by weight solution of pale yellow transparent polyester amide acid (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 obtained polyester amic acid (A) had a weight average molecular weight of 21,000.

[Synthesis Example 2] Synthesis of Epoxy Group-Containing Copolymer (B) Solution In a four-necked flask equipped with a stirrer, dehydrated and purified MMP as a polymerization solvent, glycidyl methacrylate, and other polymerizable compounds diethylene glycol dimethacrylate (NK ester 2G) Trade name; Shin-Nakamura Chemical Co., Ltd.) was charged at the following weight, and dimethyl-2,2′-azobis (2-methylpropionate) (V-601; trade name; Wako Pure Chemical) as a polymerization initiator. Kogyo Co., Ltd.) was charged at the following weight and stirred at 110 ° C. for 2 hours under a dry nitrogen stream.
MMP 31.50g
Glycidyl methacrylate 12.15g
Diethylene glycol dimethacrylate 1.35g
V-601 2.03g

  The solution was cooled to room temperature to obtain a 30% by weight solution of the epoxy group-containing copolymer (B). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the epoxy group-containing copolymer (B) obtained had a weight average molecular weight of 4,000.

[Example 1]
A 1000-ml separable flask equipped with a stirring blade was purged with nitrogen, and 40.00 g of the polyesteramic acid (A) solution obtained in Synthesis Example 1 was added to the flask as a compound having a polymerizable double bond. 12.00 g, AA-6 1.2 g, photopolymerization initiator NCI-930 0.96 g, epoxy compound EHPE3150 12.00 g, epoxy hardener trimellitic anhydride (hereinafter “TMA”) And 3.92 g of 3-glycidoxypropyltrimethoxysilane (trade name; Silaace S510, JNC Corporation) as an additive, and NT-200 (trade name; Toyo Gosei Co., Ltd.) as an additive. 0.12 g and 0.20 g of ADK STAB AO-60 (trade name; ADEKA Co., Ltd.), dehydrated and purified as solvent And MMP and 55.2 g, and MBA and 20.8g were charged, and 3hr stirring at room temperature, and uniformly dissolved therein. Then, 0.05 g of MegaFuck F-556 (trade name; DIC Corporation) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 μm) to prepare a photosensitive composition.

This photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and pre-baked on a 90 ° C. hot plate for 2 minutes. Next, it exposed using the proximity exposure machine TME-150PRC (brand name; Topcon Corporation) in the air. The exposure amount was 30 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name; Ushio Corporation) and a light receiver UVD-365PD (trade name; Ushio Corporation). The exposed coating film was subjected to paddle development for 1 minute using a 25 ° C. aqueous potassium hydroxide solution, washed with pure water for 20 seconds, and then dried on a 100 ° C. hot plate for 2 minutes. Furthermore, it post-baked for 30 minutes at 230 degreeC, and obtained the glass substrate with a cured film with a film thickness of 1.5 micrometers.

  With respect to the cured film thus obtained, the characteristics were evaluated with respect to the residual film ratio after development, heat resistance, transparency, adhesion, resolution, and flatness.

[Evaluation method of residual film ratio after development]
Using a step, surface roughness and fine shape measuring device (trade name; P-16, KLA TENCOR Co., Ltd.), the film thickness before development and the film thickness after development of the glass substrate with the cured film were measured. The residual film ratio after development was calculated by the calculation formula. The case where the post-development residual film ratio was 80% or more was rated as ◯, and the case where the post-development residual film ratio was less than 80% was rated as x.

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

[Evaluation method of heat resistance]
After the obtained glass substrate 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, the remaining film rate was calculated by the following formula, and the heat resistance was evaluated. . P-16 was used for the measurement of film thickness. The case where the remaining film ratio after heating was 95% or more was evaluated as ◯, and the case where the remaining film ratio after heating was less than 95% was evaluated as x.

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

[Transparency evaluation method]
In the obtained glass substrate with a cured film, the transmittance of the cured film alone at a wavelength of 400 nm was measured by an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, JASCO Corporation), and transparency was obtained. Evaluated. The case where the transmittance was 95% or more was rated as ○, and the case where the transmittance was less than 95% was rated as ×.

[Adhesion evaluation method]
For evaluation of adhesion, an ITO substrate with a cured film was used. The ITO substrate is a substrate in which ITO is formed on glass. The adhesion was evaluated by a crosscut method according to JIS K 5600-5-6. No. 56 (trade name; 3M Corporation) was used. Observation with a microscope was performed, and the case of classification 0 to 1 was marked with ◯, and the case of classification 2 to 5 was marked with x.

[Production of resolution evaluation substrate]
Next, the photosensitive composition was spin-coated on a glass substrate at 900 rpm for 10 seconds, and prebaked on an 80 ° C. hot plate for 2 minutes. Then, exposure was performed with an exposure gap of 100 μm using a proximity exposure machine TME-150PRC through a mask having a hole and line pattern with a width of 50 μm in air. The exposure amount was 30 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 and a light receiver UVD-365PD. The exposed coating film was subjected to paddle development at 25 ° C. for 1 minute using an aqueous potassium hydroxide solution to remove unexposed portions. The developed 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 post-baked for 30 minutes at 230 degreeC in oven, and obtained the glass substrate with a patterned cured film with a film thickness of 1.5 micrometers.

  The characteristics of the cured film thus obtained were evaluated for resolution.

[Resolution evaluation method]
The obtained glass substrate with a patterned cured film was observed with a 1,000-fold optical microscope, and the resolution of holes and line patterns corresponding to a mask size of 50 μm width was evaluated. The case where the hole and line pattern was resolved was indicated as “◯”, and the case where the hole and line pattern was not resolved was designated as “X”.

[Fabrication of flatness evaluation substrate]
Next, the photosensitive composition was spin-coated at 900 rpm for 10 seconds on a pigment-dispersed color filter (hereinafter abbreviated as CF) substrate using a resin black matrix having a maximum step of about 0.8 μm, and 2 on an 80 ° C. hot plate. Pre-baked for a minute. Next, it exposed using proximity exposure machine TME-150PRC (brand name; Topcon Corporation). The exposure amount was 30 mJ / cm ^{2 as} measured by an integrated light meter UIT-102 (trade name; Ushio Corporation) and a light receiver UVD-365PD (trade name; Ushio Corporation). The exposed coating film was subjected to paddle development at 25 ° C. for 1 minute using an aqueous potassium hydroxide solution, then the coating film was washed with pure water for 20 seconds, and then dried on a 100 ° C. hot plate for 2 minutes. Furthermore, it was post-baked at 230 ° C. for 30 minutes in an oven to obtain a CF with a cured film having a thickness of 1.5 μm.

  The properties of the cured film thus obtained were evaluated for flatness.

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

[Examples 2 to 5]
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.

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

Hereinafter, the evaluation results of the cured films of Examples 1 to 5 are collectively shown in Table 3, and the evaluation results of the cured films of Comparative Examples 1 and 2 are collectively shown in Table 4, respectively.

  As is apparent from the results shown in Tables 3 to 4, the cured films of Examples 1 to 5 are excellent in heat resistance, transparency, adhesiveness, and flatness, and the remaining film ratio and resolution after development. It can be seen that all points including sex are balanced. On the other hand, the cured films of Comparative Examples 1 and 2 do not have “◯” for all the evaluation items. As described above, a compound having a polymerizable double bond is within the scope of the present invention using a polyester amic acid obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components. All the characteristics could be satisfied.

  The cured film obtained from the photosensitive composition of the present invention is excellent in properties as an optical material such as adhesion, heat resistance, transparency, flatness and resolution. And a protective film such as various optical materials such as a light receiving element, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (13)

A photosensitive composition comprising a polyester amic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent;
The polyester amic acid is reacted with X moles of tetracarboxylic dianhydride, Y moles of diamine and Z moles of polyvalent hydroxy compounds in a ratio such that the relationship of the following formulas (1) and (2) is satisfied. And having a structural unit represented by the following formula (3) and a structural unit represented by the formula (4);
The compound having a polymerizable double bond includes a compound having a molecular weight of less than 1,000 having two or more polymerizable double bonds per molecule, and a compound having a molecular weight of 1,000 or more having a polymerizable double bond,
The weight of the compound having a molecular weight of 1,000 or more having a polymerizable double bond is 1 to 50% by weight based on the total weight of the compound having a polymerizable double bond;
The total amount of the compound having a polymerizable double bond is 20 to 300 parts by weight, the total amount of the epoxy compound is 20 to 200 parts by weight, and the total amount of the photopolymerization initiator is 100 parts by weight of the polyester amic acid. 1 to 60 parts by weight of a photosensitive composition;

0.2 ≦ Z / Y ≦ 8.0 (1)
0.2 ≦ (Y + Z) /X≦5.0 (2)

In Formula (3) and Formula (4), R ¹ is a residue obtained by removing two —CO—O—CO— from tetracarboxylic dianhydride, and R ² is a residue obtained by removing two —NH ₂ from diamine. R ³ is a residue obtained by removing two —OH from a polyvalent hydroxy compound.   The photosensitive composition of Claim 1 in which the raw material component of the said polyester amide acid contains a monohydroxy compound further.   The monohydroxy compound is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. Photosensitive composition.   The photosensitive composition of any one of Claims 1-3 whose weight average molecular weights of the said polyester amide acid are 1,000-200,000. The tetracarboxylic dianhydride is 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2- [Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and ethylene glycol bis (anhydrotrimellitate) One or more;
The diamine is one or more selected from 3,3′-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;
The polyvalent hydroxy compound is ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2, One or more selected from 2-bis (4-hydroxycyclohexyl) propane, 4,4′-dihydroxydicyclohexyl and tris (2-hydroxyethyl) isocyanurate;
Compounds having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule are dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified tri Containing at least 50% by weight of at least one selected from acrylates and polybasic acid-modified (meth) acrylic oligomers with respect to the total weight of the compound having a molecular weight of less than 1,000 containing two or more polymerizable double bonds per molecule And
The compound having a polymerizable double bond and a molecular weight of 1,000 or more is a macromonomer;
The photopolymerization initiator is one or more selected from α-aminoalkylphenone series, acylphosphine oxide series, and oxime ester series photopolymerization initiators;
And the epoxy curing agent is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole,
The photosensitive composition of any one of Claims 1-4. The tetracarboxylic dianhydride is at least one selected from 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride ;
The diamine is 3,3′-diaminodiphenylsulfone;
The polyvalent hydroxy compound is 1,4-butanediol;
The monohydroxy compound is benzyl alcohol;
One or more compounds selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified (meth) acrylic oligomer, wherein the compound having a molecular weight of less than 1,000 and containing two or more polymerizable double bonds per molecule Is;
The compound having a polymerizable double bond and a molecular weight of 1,000 or more is a methacryloylated polymethyl methacrylate oligomer;
The photopolymerization initiator is 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl],-1- (O-acetyloxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- One or more selected from (O-acetyloxime) is contained in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator;
The epoxy curing agent is one or more selected from trimellitic anhydride and 2-undecylimidazole; and
Furthermore, the photosensitive composition of any one of Claims 2-5 containing 1 or more types selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.   The cured film obtained from the photosensitive composition of any one of Claims 1-6.   A color filter using the cured film according to claim 7 as a protective film.   A display element using the color filter according to claim 8.   A solid-state imaging device using the color filter according to claim 8.   The display element using the cured film of Claim 7 as a transparent insulating film formed between TFT and a transparent electrode.   The display element using the cured film of Claim 7 as a transparent insulating film formed between a transparent electrode and alignment film.   The LED light-emitting body which used the cured film of Claim 7 as a protective film.