JP2018169604A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition that gives a cured film having excellent transparency, heat resistance, surface smoothness, resolution, and chemical resistance without requiring an organic solvent of high polarity, a cured film formed of the photosensitive composition, and an electronic component having the cured film.SOLUTION: A photosensitive composition contains a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), a polymer having an epoxy group with a weight average molecular weight of 3,000-50,000 (D), an epoxy compound that contains 2-10 epoxy groups per molecule, with a weight average molecular weight of less than 3,000 (E), an epoxy curing agent (F), and a molecular weight modifier (G).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 devices such as display devices represented by flat panel displays, various chemical treatments such as organic solvents, acids, alkaline solutions, etc. are performed, and when the wiring electrode is formed by sputtering, the surface is It may be heated locally to a high temperature. Therefore, a surface protective film may be provided for the purpose of preventing deterioration, damage, and alteration of the surface of the element. These protective films are required to have various characteristics that can withstand various treatments during the manufacturing process as described above. Specifically, transparency, flatness, light resistance, scratch resistance, water resistance, adhesion to an underlying substrate such as glass, and chemical resistance such as heat resistance, solvent resistance, acid resistance, alkali resistance, etc. Sex etc. are required.

  In recent years, touch panels, for which demand has been increasing, have been made thinner and lighter, and as a result, various characteristics such as adhesion to substrates, transparency, flatness, and heat resistance, which have been conventionally required for insulating materials. In addition to the above, developability is required such that the electrodes can be accurately formed without gaps between the electrodes. In addition, when the manufacturing process of depositing ITO on the insulating film and partially etching to form the electrode is performed once or a plurality of times, resistance to the ITO etching solution is also necessary.

  The types of curable compositions for forming these protective films and insulating 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, a 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 a thermosetting composition.

  In recent years, the need for protective films that require heat resistance, solvent resistance, and chemical resistance has increased, and the need for protective films that require fine pattern shapes has also increased. From this, the photosensitive composition which can form the protective film excellent in heat resistance, solvent resistance, and chemical resistance and can form a fine pattern is calculated | required.

  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.

  Examples of using the photosensitive composition for the protective film of the color filter include Patent Document 4 and Patent Document 5, and the present inventors use the photosensitive composition described in these documents to apply the protective film. As a result of the formation, the formed pattern is not fully satisfactory, and further improvements are desired.

  When the photosensitive composition is used for the protective film of the ITO electrode in the multilayer wiring board, resistance to the ITO etching solution is necessary, but Patent Document 5 does not mention resistance to the ITO etching solution.

  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 JP, 2006-103010, A

  An object of the present invention is to provide a photosensitive composition that does not require a highly polar organic solvent and provides a cured film excellent in transparency, heat resistance, flatness, resolution, and chemical resistance. . Moreover, it is providing the cured film formed with the said photosensitive composition, and also providing the electronic component which has the said cured film.

As a result of intensive studies to solve the above problems, the present inventors have obtained a polyester amic acid obtained from the reaction of a compound containing tetracarboxylic dianhydride, diamine and a polyvalent hydroxy compound, a compound having a polymerizable double bond The present invention is completed by finding that the above object can be achieved by a composition comprising a photopolymerization initiator, an epoxy compound, an epoxy curing agent and a molecular weight modifier, and a cured film obtained by curing the composition. It came to.
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] Polyesteramic acid (A), compound (B) having a polymerizable double bond, photopolymerization initiator (C), polymer (D) having an epoxy group, epoxy compound (E), epoxy curing agent ( F) and a photosensitive composition comprising a molecular weight modifier (G);
In the polyester amic acid (A), X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound are expressed by the following formulas (1) and (2). Comprising a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4);
The compound (B) having a polymerizable double bond contains two or more polymerizable double bonds per molecule;
The polymer (D) having an epoxy group has a weight average molecular weight of 3,000 to 50,000;
The epoxy compound (E) contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000;
The total amount of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the polyester amic acid (A) is 20 to 300 parts by weight, and the polymer (D) having the epoxy group and the epoxy compound The total amount of (E) is 20 to 200 parts by weight;
A photosensitive composition, wherein the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier (G);

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 polyester amic acid (A) has a weight average molecular weight of 1,000 to 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;
The compound (B) having a polymerizable double bond is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified triacrylate and polybasic acid modified (meth). Containing at least 50% by weight of at least one selected from acrylic oligomers based on the total weight of the compound having a polymerizable double bond;
The photopolymerization initiator (C) is at least one selected from α-aminoalkylphenone series, acylphosphine oxide series, and oxime ester series photopolymerization initiators;
The copolymer (D) having an epoxy group is a copolymer having an epoxy group which is a reaction product from a mixture of a radical polymerizable monomer (d1) having an epoxy group and a radical polymerizable monomer (d2) other than (d1). A polymer; and
The epoxy curing agent (F) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole,
[1] The photosensitive composition according to any one of [3].

[5] One kind in which the radically polymerizable monomer (d1) having the epoxy group is selected from glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether Or more;
The photosensitive composition as described in the item [4], wherein the radical polymerizable monomer (d2) other than (d1) contains one or more of bifunctional (meth) acrylates.

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

[7] 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;
The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified (meth) acryl oligomer;
The bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl One or more selected from glycol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate;
The photopolymerization initiator (C) is 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2 -1 or more types selected from-(O-acetyl oxime) are contained 50weight% or more with respect to the total weight of a photoinitiator (C);
The epoxy curing agent (F) is at least one selected from trimellitic anhydride and 2-undecylimidazole; and
The photosensitive composition according to item [5], further containing at least one selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.

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

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

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

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

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

[13] A display device using the cured film according to the item [9] as a transparent insulating film formed between the TFT and the transparent electrode.

[14] A display device using the cured film as described in the item [9] as a transparent insulating film formed between the TFT and the alignment film.

[15] An LED light emitter using the cured film as described in the item [9] as a protective film.

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

  The photosensitive composition according to a preferred embodiment of the present invention does not require a highly polar organic solvent and can form a cured film excellent in transparency, heat resistance, flatness, resolution, and chemical resistance. Thus, when used as a color filter protective film of a display element, display quality and reliability can be improved. 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 comprises a polyester amide acid (A) obtained by reacting tetracarboxylic dianhydride, diamine and a polyvalent hydroxy compound as essential raw material components, a polymerizable double bond. (B), a photopolymerization initiator (C), a polymer having an epoxy group (D), 2-10 epoxy groups per molecule, and a weight average molecular weight of 3,000. It is a composition containing an epoxy compound (E), an epoxy curing agent (F) and a molecular weight modifier (G) which are less than The compound (B) having a polymerizable double bond is 20 to 300 parts by weight with respect to 100 parts by weight of the polyester amic acid (A), and the total amount of the polymer (D) having an epoxy group and the epoxy compound (E) 20 to 200 parts by weight, the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier (G) It is. Moreover, 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 (A)
Polyester amide acid is obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components. 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 has a structural unit represented by the following formula (3) and a structural unit represented by the 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.

  At least a solvent is required for the synthesis of the polyester amide acid, and this solvent may be left as it is, and it may be a liquid or gel photosensitive composition considering handling properties, etc. It is good also as a solid composition in consideration of the above. 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 the 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, a diamine is used as a material for obtaining a 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 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 the compatibility when a polyester amic acid formed using these, a polymer having an epoxy group, an epoxy compound and an epoxy curing agent are mixed, and the applicability of the photosensitive composition on a color filter, The use of benzyl alcohol is particularly preferred for the hydroxy compound.

  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 (B) having a polymerizable double bond
1-2-1. Compound having two or more polymerizable double bonds per molecule The compound having a polymerizable double bond used in the present invention is not particularly limited, but has two or more polymerizable double bonds per molecule. A compound is preferred. 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 two or more polymerizable double bonds contained in the photosensitive composition of the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene 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, trimethylolpropane tri (meth) ) Acrylate, ethylene oxide modified trimethylolpropane tri ) Acrylate, 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 cyclohexyl di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, caprolact 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 pentaerythritol 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, dipentaerythritol Hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, many Base 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 tetraacrylate, polyester Ester pentaacrylate, polyester hexaacrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified 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] isocyanurate, (meth) Acrylic isocyanurate, phenylglycidyl ether acrylate hexamethylene diisocyanate urea Prepolymer, phenylglycidyl ether acrylate Toluene diisocyanate Urethane prepolymer, Pentaerythritol triacrylate Hexamethylene diisocyanate Urethane prepolymer, Pentaerythritol triacrylate Toluene diisocyanate Urethane prepolymer, Pentaerythritol triacrylate Isophorone diisocyanate Urethane prepolymer, Dipentaerythritol pentaacrylate Examples include hexamethylene diisocyanate urethane prepolymer, non-yellowing type oligourethane acrylate, and carboxylic acid-containing urethane acrylate oligomer.

  As the compound having two or more polymerizable double bonds per molecule, the above compounds may be used alone or two or more of them may be used in combination.

  Among compounds having two or more polymerizable double bonds per molecule, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modification ( Use of a (meth) acrylic oligomer, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, or a mixture thereof is preferable from the viewpoint of heat resistance and chemical 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 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 the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronics M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 (30-60 wt%), M-452 (25 to 40% by weight) and M-450 (less than 10% by weight, hereinafter abbreviated as “M-450”) (all trade names; Toagosei Co., Ltd., the content in parenthesis is in the mixture) Catalog content value of the content of pentaerythritol triacrylate). 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%). , Hereinafter abbreviated as “M-402”), M-404 (30-40 wt%), M-406 (25-35 wt%), and M-405 (10-20 wt%) (all trade names; Toagosei Co., Ltd., the content in parenthesis is the catalog 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.). Specific examples of a mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate are Aronix M-313 (30 to 40% by weight) and M-315 (3 to 13% by weight, hereinafter abbreviated as “M-315”). (All are trade names; Toagosei Co., Ltd., the content in parentheses is the catalog listed value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture).

1-2-2. 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, (meth) acrylic acid 4-hydroxyphenyl and p-hydroxy (meth) acrylanilide are preferable because of good resolution.

1-3. Photopolymerization initiator (C)
The photopolymerization initiator contained in the photosensitive composition of the present invention is a composition containing polyester amic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent, and a molecular weight modifier. 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 OXE-01, BASF Japan Ltd.), Etanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazo -3-yl] -1- (O-acetyloxime) (for example, trade name: IRGACURE OXE-02, BASF Japan Ltd.), OXE-03 (trade name; BASF Japan Ltd.), OXE-04 (trade name) BASF Japan Ltd.), 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) (for example, trade name; Adeka Arcles) NCI-930, ADEKA Corporation), 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 (trichloro) Methyl) -s-triazine, 4- [pN, 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) benzoxazo 2, 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'-bi Imidazole, 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-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like.

  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 viewpoint of the sensitivity of the coating film during exposure and the 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 this specification, all the thin films in the steps from the preheating to the drying are referred to as “coating films”, and for example, by using the notation “coating film at the time of exposure” and “coating film after development” Let us indicate whether it is a stage coating.

  Among the photopolymerization initiators, 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. More preferred. 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. Polymer having epoxy group (D)
The polymer having an epoxy group used in the present invention has a weight average molecular weight of 3,000 or more. By adding an epoxy compound to the photosensitive composition of the present invention, the heat resistance, solvent resistance, and chemical resistance of the cured film can be enhanced.

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

  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 chemical 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 polymer having an epoxy group obtained by reacting with glycidyl (meth) acrylate with the polyester amide acid is improved. It is preferable that the bifunctional (meth) acrylate is contained in an amount of 1 to 30 parts by weight in all monomers that are raw materials for the polymer having an epoxy group, from the viewpoints of flatness, heat resistance, and chemical resistance.

  The polymer having an epoxy group 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.

  One type or two or more types of other radical polymerizable monomers may be used.

  The weight average molecular weight of the polymer having an epoxy group 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, heat resistance, and chemical resistance can be obtained.

1-5-1. Solvent used for the synthesis reaction of a polymer having an epoxy group At least a solvent is required for the synthesis of a polymer having an epoxy group obtained by reacting glycidyl (meth) acrylate and bifunctional (meth) acrylate as essential raw material components. is necessary.

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

  These solvents can be used alone or as a mixed solvent of two or more. Moreover, if it is a ratio of 30 weight% or less with respect to the whole quantity of a solvent, in addition to the said solvent, another solvent can also be mixed and used.

1-5-2. Method for synthesizing polymer having epoxy group The method for synthesizing a polymer having an epoxy group is not particularly limited, but radical polymerization in a solution using a solvent is preferable. When the reaction solvent is used in an amount of 100 parts by weight or more with respect to a total of 100 parts by weight of glycidyl (meth) acrylate, bifunctional (meth) acrylate, and other radical polymerizable monomers used as necessary, the reaction proceeds smoothly. Therefore, it is preferable. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 ° C to 150 ° C. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

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

  The polymer having an epoxy group may be used as an epoxy compound solution considering the handling properties by leaving the solvent used for synthesis as it is, or as a solid epoxy compound considering the transportability by removing this solvent. Good.

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

  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] Mixture with 2-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 Materials Corporation), 1 , 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2-bis (hydroxymethyl) ) -1-Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (eg, trade name; EHPE-3150) It can be exemplified Co., Ltd. Daicel), and the like.

  The total amount of the polymer (D) having an epoxy group and the epoxy compound (E) is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the polyester amide acid (A) because the flatness is good.

1-6. Epoxy curing agent (F)
An epoxy curing agent is used in the photosensitive composition of the present invention in order to improve flatness, chemical 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.

1-7. Molecular weight regulator (G)
In the photosensitive composition of the present invention, a molecular weight modifier is used 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, and phenothiazine.

  Specific examples of the molecular weight modifier include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, 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 and the like.

  A molecular weight modifier may be used independently and may be used in combination of 2 or more. Among the molecular weight regulators, naphthoquinone molecular weight regulators are preferred from the standpoint of exhibiting excellent resolution.

  Among the molecular weight modifiers, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferable from the viewpoint of resolution. In addition, it is preferable from the viewpoint of resolution that the content of the photopolymerization initiator is more than 5.0 times and less than 30 times the content of the molecular weight modifier. It is more preferable to contain the molecular weight regulator so that the content of the polymerization initiator is more than 5.1 times and less than 20 times the content of the molecular weight regulator. It is further preferable to contain the molecular weight regulator so that the content of the photopolymerization initiator is more than 5.2 times the content of the molecular weight regulator and 10 times or less.

1-8. Polyester amide acid, compound having polymerizable double bond, photopolymerization initiator, polymer having epoxy group, ratio of epoxy compound, epoxy curing agent and molecular weight modifier In the photosensitive composition of the present invention, polyester amide acid 100 The ratio of the compound having a polymerizable double bond to 20 parts by weight is 20 to 300 parts by weight. When the ratio of the compound having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance and remaining film ratio after development is good. More preferably, the compound having a polymerizable double bond is in the range of 100 to 300 parts by weight.

  The ratio of the photopolymerization initiator to 100 parts by weight of the polyester amide acid is 2 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.

  In the photosensitive composition of the present invention, the ratio of the total amount of the polymer having an epoxy group and the epoxy compound to 100 parts by weight of the polyester amide acid is 20 to 200 parts by weight. When the ratio of the total amount of the polymer having an epoxy group and the epoxy compound is within this range, the balance between heat resistance and flatness is good. The total amount of the polymer having an epoxy group and 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 total amount of the polymer having an epoxy group and 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 total amount of the polymer having an epoxy group and 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. It is more preferable to add the carboxylic acid anhydride group or the carboxyl group so that the equivalent amount of the carboxylic acid anhydride group or carboxyl group is 0.15 to 0.8 times, since the chemical resistance is further improved.

1-9. Other Components Various additives can be added to the photosensitive composition of the present invention in order to improve coating uniformity and adhesion. Additives include solvents, photoacid generators, anionic, cationic, nonionic, fluorine or silicon surfactants, adhesion improvers, hindered phenols, hindered amines, phosphorus compounds, sulfur compounds Mainly mentioned are antioxidants.

1-9-1. 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.

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

  Specific examples of 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.

1-9-3. 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.), Disperbak-161, Disperbak-162, Disperbak-163, Dispersake-164, Dispersake-166, Dispersake-170, Dispersake-180 , Disper Bake-181, Disper Bake-182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (All trade names; Big Chemie Japan Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF-50-100CS (all trade names; Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade name) ; GC Seimi Chemical Co., Ltd.), Aftergent 222F, Aftergent 208G, Aftergent 251, Aftergent 710FL, Aftergent 710FM, Aftergent 710FS, Aftergent 601AD, Aftergent 650A, FTX-218 (all trade names: Inc. Neos), Mega Fuck F-171, Mega Fuck F-177, Mega Fuck F-410, Mega Fuck F-430, Mega Fuck F-444, Mega Fuck F-472SF, Mega Fuck F-475, Mega Fuck F-477 , Megafuck F-552, Megafuck F-553, Megafuck F-554, Megafuck F-555, Megafuck F-556, Megafuck F-558, Megafuck F-559, Megafuck R-94, Gafuck RS-75, Megafuck RS-72-K, Megafuck RS-76-NS, Megafuck 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 Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, fluoroalkylammonium iodide, fluoroalkyl Betaine, fluoroalkyl sulfonate, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium Salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxy Ethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, Sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate DOO, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonates, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

  Among these surfactants, BYK-306, BYK-342, BYK-346, 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, Fluoro When it is at least one selected from alkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amino sulfonate, It is preferable because the coating uniformity of the photosensitive composition is increased.

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

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

  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), 3-glycidyloxypropyl Silane coupling agents such as polymers of trimethoxysilane (for example, trade name: COATOSIL MP 200, Momentive Performance Materials Godo Co., Ltd.), acetoalkoxyaluminum diisopropylate Examples thereof include aluminum coupling agents such as carbonates and titanate coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

  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.

1-9-5. Macromonomer having a polymerizable double bond The photosensitive composition of the present invention may further contain a macromonomer having a polymerizable double bond from the viewpoint of adhesion described in the previous section.

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

  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).

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

  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, Irganox565DD (all trade name; BASF Japan stock Company), ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all are trade names) ; ADEKA Corporation). Among these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-10. 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 is a mixture of polyester amic acid, a compound having a polymerizable double bond, a polymer having an epoxy group, an epoxy compound, an epoxy curing agent and a molecular weight modifier. Depending on the intended properties, a solvent, a coupling agent, a surfactant, and other additives may be further selected and added as necessary, and they may be uniformly mixed and dissolved.

  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 further has a 1) polyamic acid portion of the polyester amic acid to form a imide bond upon heating, and 2) a polymer in which the carboxylic acid of the polyester amic acid has an epoxy group. It is very tough because of its high molecular weight by reaction with, 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, an Example, and a comparative example demonstrate this invention concretely, this invention is not limited at all by these Examples. In addition, the abbreviation of various materials in Tables 1-2 is demonstrated below. M-402 is a compound having a polymerizable double bond Aronix M-402 (trade name; Toagosei Co., Ltd.), NCI-930 is a photopolymerization initiator Adeka Arcles NCI-930 (trade name; ADEKA Corporation), VG3101L Is an epoxy compound TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE3150 is an epoxy compound EHPE3150 (trade name; Daicel Corporation), TMA is an epoxy curing agent trimellitic anhydride, S510 is an adhesion improver, and Sira Ace S510 (product Name: JNC Corporation), MP 200 is coupling agent COATOSIL MP 200 (trade name; Momentive Performance Materials LLC), AO-60 is antioxidant ADKSTAB AO-60 (trade name; Corporation) ADEKA), F-556 is a surfactant, Mega-Fac F-556 (trade name; DIC Corporation), MMP is a solvent, methyl 3-methoxypropionate, PGMEA is a solvent, propylene glycol monomethyl ether acetate, and EDM is a solvent, diethylene glycol ethyl Methyl ether.

Note that VG3101L is 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane ( Molecular weight = 593) 90% by weight and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (2,3-epoxy) Propoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol (molecular weight = 1,129) 10% by weight, EHPE3150 is a compound represented by the molecular formula C ₁₂₆ H ₁₉₄ O ₃₃ Yes, the molecular weight is 2,237 (both refer to the product safety data sheet).

  First, a polyester amic acid (A) solution comprising a reaction product such as tetracarboxylic dianhydride, diamine, and polyvalent hydroxy compound, and a solution of an epoxy group-containing polymer (D) are synthesized as shown below. (Synthesis Examples 1 and 2).

[Synthesis Example 1] Synthesis of polyester amic acid (A) solution In a four-necked flask equipped with a stirrer, dehydrated and purified PGMEA, BT-100, SMA1000P (trade name: styrene / maleic anhydride copolymer, Kawa Crude Chemical Co., Ltd.) ), 1,4-butanediol, and benzyl alcohol in the order of the following weights, and stirred at 125 ° C. for 3 hours under a dry nitrogen stream.
PGMEA 481.37g
BT-100 34.47g
SMA1000P 164.11g
1,4-butanediol 10.45 g
Benzyl alcohol 50.17g

Thereafter, the reaction solution was cooled to 25 ° C., 3,3′-diaminodiphenylsulfone (hereinafter abbreviated as DDS) and PGMEA were added in the following weights, stirred at 20-30 ° C. for 2 hours, and then at 125 ° C. Stir for 2 hours.
DDS 10.80g
PGMEA 148.63g

[Z / Y = 2.7, (Y + Z) /X=0.9]

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

[Synthesis Example 2] Synthesis of Polymer (D) Solution Having Epoxy Group In a four-necked flask with a stirrer, MMP dehydrated and purified as a polymerization solvent, glycidyl methacrylate as a radical polymerizable compound (a1) having an epoxy group, and others As a polymerizable compound (a2), diethylene glycol dimethacrylate (NK ester 2G; trade name: Shin-Nakamura Chemical Co., Ltd.) was charged in the following weight, and dimethyl-2,2′-azobis (2-methyl) was further added as a polymerization initiator. Propionate) (V-601; trade name; Wako Pure Chemical Industries, 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 30.0% by weight solution of the polymer (D) having an epoxy group. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (D) having an epoxy group was 4,000.

[Example 1]
A 1000-ml separable flask with stirring blades 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. 60.00 g, 2-hydroxy-1,4-naphthoquinone 0.06 g as a molecular weight regulator, 1.2 g NCI-930 as a photopolymerization initiator, and 12.00 g polymer (D) solution having an epoxy group 1.2 g of EHPE3150 as an epoxy compound, 2.0 g of trimellitic anhydride (hereinafter abbreviated as “TMA”) as an epoxy curing agent, and a polymer of 3-glycidyloxypropyltrimethoxysilane as an additive (trade name) COATOSIL MP 200, Momentive Performance Materials LLC), 1.92g, NT 200 (trade name; Toyo Gosei Kogyo Co., Ltd.) 0.64 g, ADKSTAB AO-60 (trade name; ADEKA Co., Ltd.) 0.06 g, dehydrated and purified MMP 4.1 g, and PGMEA 22. 0 g was charged and stirred at room temperature for 3 hours to dissolve uniformly. Next, 0.02 g of Megafac 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.

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

[Comparative Examples 1-4]
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.

Each of the photosensitive compositions obtained above was spin-coated on a glass substrate at 550 rpm for 10 seconds, and prebaked on a hot plate at 100 ° C. for 80 seconds. 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 developed for 40 seconds using a buffer solution of sodium carbonate / sodium hydrogen carbonate at 27 ° C., 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, and obtained the glass substrate (1) with a cured film with a film thickness of 3.0 micrometers.

  Except having replaced the said glass substrate with the glass substrate with ITO, according to the preparation methods of the said glass substrate with a cured film (1), the glass substrate with a cured film (2) was obtained from each photosensitive composition. .

  By using the above-described glass substrate with a cured film (1), the residual film ratio after development, adhesion, chemical resistance, heat resistance, and transparency of the glass substrate with a cured film (2) are as follows. Used to evaluate adhesion and chemical resistance.

[Evaluation method of residual film ratio after development]
Using a step / surface roughness / 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 cured film (1) are measured. The post-development residual film ratio was calculated according to the following 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

[Production of resolution evaluation substrate]
Next, the photosensitive composition was spin coated on a glass substrate at 550 rpm for 10 seconds, and prebaked on a hot plate at 100 ° C. for 80 seconds. Then, exposure was performed with an exposure gap of 100 μm using a proximity exposure machine TME-150PRC through a mask having a 30 μm wide hole and line pattern in the 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 developed for 40 seconds using a buffer solution of sodium carbonate / sodium hydrogen carbonate at 27 ° C., washed with pure water for 20 seconds, and then dried on a hot plate at 100 ° C. for 2 minutes. Furthermore, it post-baked at 230 degreeC for 30 minute (s) in oven, and obtained the glass substrate (3) with a cured film with a film thickness of 3.0 micrometers.

  The resolution of the cured film thus obtained was evaluated.

[Resolution evaluation method]
The obtained glass substrate (3) with a 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 30 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”.

[Evaluation method of heat resistance]
After reheating the glass substrate with cured film (1) obtained above at 230 ° C. for 1 hour, the film thickness before heating and the film thickness after heating are measured, and the remaining film ratio after heating is calculated by the following formula. The heat resistance was evaluated. P-16 was used for the measurement of film thickness. The case where the residual film ratio after heating was 95% or more was rated as ◯, and the case where the residual 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 glass substrate with a cured film (1) obtained above, the transmittance of the cured film alone at a wavelength of 400 nm was measured with an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, JASCO Corporation). And the transparency was 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]
Adhesion was evaluated according to JIS K 5600-5-6 (cross cut test). That is, the glass substrates with cured film (1) and (2) obtained above were cut so that 100 square cells of 1 mm × 1 mm were formed, and cellophane tape (manufactured by 3M) was formed on the cells. , Scotch (registered trademark) cellophane tape No. 610) was applied and then peeled off. ○ when the cured film in the cell is not peeled off at all, △ when less than one third of the cured film in the cell is peeled, Δ when more than one third is peeled off Is x.

[Chemical resistance evaluation method]
The glass substrates with cured film (1) and (2) obtained above were immersed in an ITO etching solution (trade name; ITO-301, manufactured by Kanto Chemical Co., Ltd.) at 25 ° C. for 6 minutes, washed with pure water, Wipe off. Furthermore, cuts are made so that 100 square squares of 1 mm × 1 mm are formed, and a cellophane tape (manufactured by 3M, Scotch (registered trademark) cellophane tape No. 610) is applied on the squares and then peeled off. A peel test was performed to evaluate chemical resistance. ○ when the cured film in the cell is not peeled off at all, △ when less than one third of the cured film in the cell is peeled, Δ when more than one third is peeled off Is x.

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

  As is clear from the results shown in Table 3, the cured films of Examples 1 to 4 are excellent in residual film ratio after development, resolution, heat resistance, transparency, adhesion, and chemical resistance. On the other hand, none of the cured films of Comparative Examples 1 to 4 is “◯”. As described above, when using the polyester amic acid obtained by reacting tetracarboxylic dianhydride, diamine and polyvalent hydroxy compound as essential raw material components, the molecular weight of the epoxy compound is within the scope of the present invention, 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 transparency, heat resistance, flatness, resolution and chemical resistance. It can be used as a protective film such as various optical materials such as an element and 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 (16)

Polyester amic acid (A), compound having polymerizable double bond (B), photopolymerization initiator (C), polymer having epoxy group (D), epoxy compound (E), epoxy curing agent (F), And a photosensitive composition comprising a molecular weight modifier (G);
In the polyester amic acid (A), X moles of tetracarboxylic dianhydride, Y moles of diamine, and Z moles of polyvalent hydroxy compound are expressed by the following formulas (1) and (2). Comprising a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4);
The compound (B) having a polymerizable double bond contains two or more polymerizable double bonds per molecule;
The polymer (D) having an epoxy group has a weight average molecular weight of 3,000 to 50,000;
The epoxy compound (E) contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000;
The total amount of the compound (B) having a polymerizable double bond with respect to 100 parts by weight of the polyester amic acid (A) is 20 to 300 parts by weight, and the polymer (D) having the epoxy group and the epoxy compound The total amount of (E) is 20 to 200 parts by weight;
A photosensitive composition, wherein the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier (G);

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 polyester amic acid (A) has a weight average molecular weight of 1,000 to 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;
The compound (B) having a polymerizable double bond is dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, isocyanuric acid ethylene oxide modified triacrylate and polybasic acid modified (meth). Containing at least 50% by weight of at least one selected from acrylic oligomers based on the total weight of the compound having a polymerizable double bond;
The photopolymerization initiator (C) is at least one selected from α-aminoalkylphenone series, acylphosphine oxide series, and oxime ester series photopolymerization initiators;
The copolymer (D) having an epoxy group is a copolymer having an epoxy group which is a reaction product from a mixture of a radical polymerizable monomer (d1) having an epoxy group and a radical polymerizable monomer (d2) other than (d1). A polymer; and
The epoxy curing agent (F) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole,
The photosensitive composition of any one of Claims 1-3. The radical polymerizable monomer (d1) having the epoxy group is at least one selected from glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether. ;
The photosensitive composition of Claim 4 in which radically polymerizable monomer (d2) other than (d1) contains 1 or more types of bifunctional (meth) acrylate.   The molecular weight modifier (G) is at least one selected from mercaptans, xanthogens, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-pentene. 2. The photosensitive composition according to item 1. 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;
The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified (meth) acryl oligomer;
The bifunctional (meth) acrylate is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl One or more selected from glycol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate;
The photopolymerization initiator (C) is 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) phenylthio] phenyl] -2 -1 or more types selected from-(O-acetyl oxime) are contained 50weight% or more with respect to the total weight of a photoinitiator (C);
The epoxy curing agent (F) is at least one selected from trimellitic anhydride and 2-undecylimidazole; and
The photosensitive composition according to claim 5, further comprising at least one selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.   The photosensitive composition of any one of Claims 1-7 whose said molecular weight modifier (G) is 1 or more types selected from naphthoquinones and hydroquinones.   The cured film obtained from the photosensitive composition of any one of Claims 1-8.   A color filter having the cured film according to claim 9 as a transparent protective film.   A display element using the color filter according to claim 10.   A solid-state imaging device using the color filter according to claim 10.   The display element using the cured film of Claim 9 as a transparent insulating film formed between TFT and a transparent electrode.   A display element using the cured film according to claim 9 as a transparent insulating film formed between the TFT and the alignment film.   The LED light-emitting body which used the cured film of Claim 9 as a protective film.   An interlayer insulating film having the cured film according to claim 9 as a transparent protective film.