KR20180108439A - Photosensitive compositions - Google Patents

Abstract

The present invention relates to a photosensitive composition comprising a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent and an inorganic fine particle, and specifically, to a photosensitive composition obtained by reacting the polyester amide acid with a tetracarboxylic dianhydride, a diamine and a polyhydric hydroxy compound as essential raw material components. With the photosensitive composition of the present invention, a cured film having excellent heat resistance, transparency, flatness, residual film ratio, resolution, and refractive index can be formed.

Description

[0001] PHOTOSENSITIVE COMPOSITIONS [0002]

The present invention relates to a photosensitive composition used in various devices, a cured film formed from the photosensitive composition, and a color filter, an insulating film, a protective film, or an optical waveguide using the cured film.

In the manufacturing process of elements such as display elements, various chemical treatments such as organic solvents, acids, and alkaline solutions are performed, or when the wiring electrodes are formed by sputtering, the surface may be locally heated to a high temperature. For this reason, a surface protective film may be formed for the purpose of preventing deterioration, damage, and alteration of the surface of various devices. These protective films are required to have various properties that can withstand various treatments in the above-described manufacturing process. Specifically, it is required to have heat resistance, chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, durability, flatness and light resistance. In addition, while high performance such as high viewing angle, fast response, high definition, and coloring of the display device is being promoted, for example, a material having improved transparency, heat resistance and solvent resistance is required when used as a color filter protective film have.

Further, in addition to satisfying each of the above-described roles, the protective film is required to have high refractive index and high transparency because it improves the light extraction efficiency when used, for example, as an optical system member of a top emission type organic EL device .

The types of the curable composition for forming these protective films are roughly classified into a photosensitive composition and a thermosetting composition. Since the thermosetting composition is completely cured by high-temperature heating at the time of film formation, volatilization generated even when heated to a high temperature in subsequent steps is small, and heat resistance is excellent. As a thermosetting protective film material having these excellent characteristics, for example, there is a polyester amide acid composition as shown in Patent Document 1. [ However, the thermosetting composition can not form a fine pattern, and in forming a fine pattern, a resist material and many additional processes are required.

On the other hand, in the case of a photosensitive composition, formation of a fine pattern is easy and moldability is excellent. The photosensitive composition is composed of a polymer, oligomer or monomer having a photopolymerizable group and a photopolymerization initiator and causes a chemical reaction by the energy of light including ultraviolet rays to cure. The photosensitive composition is subjected to processes such as coating, exposure, development, firing, etc. on the substrate to form a fine pattern.

In recent years, there has been a demand for a protective film for a photosensitive composition in easiness of pattern formation, and a photosensitive composition capable of forming a fine pattern with a higher residual film ratio (hereinafter referred to as a residual film ratio) is required. Further, in addition to being capable of forming a fine pattern with a high residual film ratio for use in an optical member, it is also demanded that the cured film has a high refractive index, high transparency, and high heat resistance.

As an example of a photosensitive composition that gives a high refractive index cured film, an example of a photosensitive composition containing inorganic fine particles has been reported as disclosed in Patent Document 2. However, in Patent Document 2, although the transmittance and the refractive index of a cured film formed from a photosensitive composition containing an acrylic resin have been disclosed, they are not sufficiently satisfactory in heat resistance, and further improvement is required.

Further, when the inorganic fine particles are added to the photosensitive composition, when the dispersibility of the inorganic fine particles to the resin contained in the photosensitive composition is poor, aggregation of the inorganic fine particles occurs, and the transmittance of the obtained cured film is lowered, And the like may occur in some cases.

Japanese Laid-Open Patent Publication No. 2008-156546 Japanese Patent Application Laid-Open No. 2014-160228

The object of the present invention is to provide a cured film excellent in heat resistance, transparency, flatness, further, particularly, residual film ratio, resolution and refractive index, for application to various applications such as color filters, insulating films, protective films or optical waveguides. Further, it is intended to provide a photosensitive composition capable of forming such a cured film.

As a result of intensive studies to solve the above problems, the present inventors have found that a composition comprising a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent and an inorganic microfine particle, And that the above object can be achieved by the cured film, and thus the present invention has been accomplished.

The present invention includes the following configuration.

[1] A photosensitive resin composition comprising a polyester amide acid (A), a polymerizable double bond-containing compound (B), a photopolymerization initiator (C), an epoxy compound (D), an epoxy curing agent (E) As a composition;

The polyester amide acid (A) is obtained by reacting X mole of tetracarboxylic dianhydride, Y mole of diamine and Z mole of polyhydric hydroxy compound at a ratio satisfying the relations of the following formulas (1) and (2) And includes a constituent unit represented by the following formula (3) and a constituent unit represented by the following formula (4);

The compound (B) having a polymerizable double bond has two or more polymerizable double bonds per molecule;

The epoxy compound (D) contains 2 to 10 epoxy groups per molecule;

The total amount of the polymerizable double bond-containing compound (B) is 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), the total amount of the epoxy compound (D) is 20 to 200 parts by weight, Composition;

0.2? Z / Y? 8.0 (1)

0.2? (Y + Z) /X? 5.0 (2)

In the formulas (3) and (4), R ¹ is a residue excluding two -CO-O-CO- from a tetracarboxylic acid dianhydride, R ² is a residue excluding two -NH ₂ from a diamine, , And R < ³ > is a residue excluding two -OH from the polyhydric hydroxy compound.

[2] The photosensitive composition according to [1], wherein the raw material component of the polyester amide acid (A) further comprises a monohydroxy compound.

[3] The method according to [1], wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, Is at least one selected from the group consisting of a halogen atom and a halogen atom.

[4] The polyester amide acid (A) has a weight average molecular weight of 1,000 to 200,000;

Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, (Dihydrocarbodiimide) is selected from 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis Is at least one;

The diamine is at least one selected from 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;

Wherein the polyhydric hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and isocyanuric acid tris (2-hydroxyethyl);

Wherein the polymerizable double bond-containing compound (B) is at least one compound selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and isocyanuric acid ethyleneoxide- At least one selected is contained in an amount of 50% by weight or more based on the total weight of the compound having a polymerizable double bond;

Wherein the epoxy compound (D) is at least one selected from the group consisting of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl- Ethyl] phenyl] phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) ] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenoxy] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3- Tris (4-hydroxyphenyl) ethane triglycidyl ether, 1,3-bis (oxiranylmethyl) propane, (1H, 3H, 5H) -triene, and 2,2-bis (hydroxymethyl) -1- The photosensitive composition according to any one of [1] to [3], wherein the photosensitive composition is at least one selected from 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol.

[5] The photopolymerization initiator according to any one of [1] to [4], wherein the photopolymerization initiator (C) is at least one selected from an α-aminoalkylphenon-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator and an oximeester- Sensitive composition.

[6] The photosensitive composition according to any one of [1] to [5], wherein the epoxy curing agent (E) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole.

[7] The method according to any one of [1] to [3], wherein the tetracarboxylic acid dianhydride is at least one selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2,3,4- One;

The diamine is 3,3'-diaminodiphenylsulfone;

The polyhydric hydroxy compound is 1,4-butanediol;

The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;

The photopolymerization initiator (C) contains a compound represented by the following formula (5) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator;

Wherein the epoxy compound (D) is at least one selected from the group consisting of 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- ] Phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenoxy] phenyl] -2- [4- [1, 2-dihydroxyphenyl] , 1-bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane;

Wherein the epoxy curing agent (E) comprises at least one selected from trimellitic anhydride and 2-undecylimidazole;

The photosensitive composition according to any one of [1] to [6], further comprising at least one solvent selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate;

Wherein R ⁴ , R ⁵ and R ⁷ are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 15 carbon atoms, An alkenyl group having 2 to 15 carbon atoms or an alkynyl group having 2 to 15 carbon atoms, and each n is independently an integer of 0 to 5.

[8] The photosensitive composition according to any one of [1] to [7], wherein the raw material of the polyester amide acid (A) comprises a styrene / maleic anhydride copolymer.

[9] The photosensitive composition according to any one of [1] to [8], wherein the inorganic fine particles (F) contain 30 to 300 parts by weight per 100 parts by weight of the polyester amide acid (A).

[10] The photosensitive composition according to any one of [1] to [9], wherein the inorganic fine particles (F) are titanium oxide or zirconia having a primary particle size of 1 to 100 nm.

[11] A cured film obtained from the photosensitive composition according to any one of [1] to [10].

[12] A color filter having the cured film described in [11] as a transparent protective film.

[13] An electronic device having the cured film according to [11].

With the above-described constitution, the photosensitive composition according to the present invention can form a cured film having excellent heat resistance, transparency, flatness, further, particularly excellent residual film ratio, resolution, and refractive index. This cured film can be applied to various applications such as a color filter, a protective film, an insulating film, and an optical waveguide.

1. Photosensitive composition

The photosensitive composition of the present invention comprises a polyester amide acid (A) obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyhydric hydroxy compound as essential raw material components, a compound (B) having a polymerizable double bond, a photopolymerization initiator C), an epoxy compound (D) containing 2 to 10 epoxy groups per molecule, an epoxy curing agent (E), and inorganic fine particles (F). The total amount of the compound (B) having a polymerizable double bond is 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), the total amount of the epoxy compound (D) is 20 to 200 parts by weight, The total amount of the inorganic fine particles (F) is 30 to 300 parts by weight.

On the other hand, the photosensitive composition according to the present invention may further contain other components in addition to the above-mentioned components in the range in which the effect of the present invention can be obtained.

1-1. The polyester amide acid (A)

The polyester amide acid (A) is obtained by reacting tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound as essential raw material components. Further, the polyester amide acid (A) is obtained by reacting X mole of tetracarboxylic dianhydride, Y mole of diamine and Z mole of polyhydric hydroxy compound at a ratio in which the relationship of the following formulas (1) and (2) .

The polyester amide acid (A) has a structural unit represented by the formula (3) and a structural unit represented by the formula (4). In the formulas (3) and (4), R ¹ is a residue excluding two -CO-O-CO- from a tetracarboxylic dianhydride and R ² is a residue excluding two -NH ₂ from a diamine . R ³ may have a polymerizable double bond.

In order to synthesize the polyester amide acid (A), at least a solvent is required, and the solvent may be left as it is to give a liquid or gel photosensitive composition in consideration of handling properties, etc. The solvent may be removed to obtain a solid composition . In the synthesis of the polyester amide acid (A), at least one compound selected from a monohydroxy compound and a styrene-maleic anhydride copolymer may be contained as a raw material if necessary. Among them, a monohydroxy compound . The synthesis of the polyester amide acid (A) may also include other compounds than those mentioned above as needed as far as the object of the present invention is not impaired as a raw material. Examples of such other raw materials include silicon-containing monoamines.

1-1-1. Tetracarboxylic dianhydride

In the present invention, a tetracarboxylic acid dianhydride is used as a material for obtaining the polyester amide acid (A). Specific examples of the preferable tetracarboxylic dianhydride include 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2 , 3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenyl Sulfone tetracarboxylic 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-di Carboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, ethylene glycol bis (anhydrotrimellitate) (TMEG-100, Shin-Nippon Rika Co., Ltd.) Cyclobutane tetracarboxylic acid dianhydride, methylcyclobutane tetracarboxylic acid dianhydride , There may be mentioned the cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane and the dianhydride. One or more of these may be used.

Among them, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride which gives good transparency to the cured film , And 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and TMEG-100 are more preferable, and 3 , 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and 1,2,3,4-butanetetracar Particularly preferred is a mixed acid dianhydride.

1-1-2. Diamine

In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). 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- (3-aminophenoxy) phenyl] Phenoxy) phenyl] hexafluoropropane. One or more of these may be used.

Among them, 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone which give good transparency to the cured film are more preferable, and 3,3'-diaminodiphenyl Sulfone is particularly preferred.

1-1-3. The polyhydric hydroxy compound

As the material for obtaining the polyester amide acid (A), a polyhydric hydroxy compound having no polymerizable double bond and / or a polyhydric hydroxy compound having a polymerizable double bond are used in the present invention.

As the polyhydric hydroxy compound having no polymerizable double bond, 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, Glycols, polypropylene glycols having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, - pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,6-hexanediol, 1,6-hexanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,2-decanediol, 1,2-decanediol, 1,2-dodecanediol, 1,2-dodecanediol, 1,12-decanediol, - dodecanediol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, Bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) sulfone), bisphenol F (bis (4- Hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, (4-hydroxyphenyl) ethanol, diethanolamine, and triethanolamine.

Specific examples of the polyhydric hydroxy compound having a polymerizable double bond include glycerin monoallyl ether, trimethylolpropane monoallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, dipentaerythritol monoallyl ether, dipentaerythritol di (Meth) acrylate, trimethylolpropane mono (meth) acrylate, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, sorbitol monoallyl ether, sorbitol diallyl ether, sorbitol triallyl ether, sorbitol tetraallyl ether, glycerin mono Acrylate, dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, pentaerythritol mono Acrylate, dipentaerythritol tetra (meta (Meth) acrylic acid modified product of sorbitol mono (meth) acrylate, sorbitol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, ethylene glycol diglycidyl ether (Meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, (meth) acrylic acid modified product of glycerin diglycidyl ether, bisphenol A diglycidyl Acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol S diglycidyl ether, (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether, S (meth) acrylic acid modified product of diglycidyl ether, (meth) acrylic acid modified product of bisphenol F diglycidyl ether, propylene oxide modified bisphenol F (Meth) acrylic acid modified product of diglycidyl ether, (meth) acrylic acid modified product of biscylenoldiglycidyl ether, (meth) acrylic acid modified product of biphenol diglycidyl ether, fluorene diphenol diglycidyl (Meth) acrylic acid modified product of cyclohexane-1,4-dimethanol diglycidyl ether, a (meth) acrylic acid modified product of hydrogenated bisphenol A diglycidyl ether, a tricyclo (Meth) acrylic acid modified product of decanedimethanol diglycidyl ether, and (meth) acrylic acid modified product of another compound containing two or more epoxy groups per molecule, and at least one of them may be used .

Among them, the compound having good solubility in a reaction solvent is preferably at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, (2-hydroxyethyl), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4- (Meth) acrylic acid modified product of ethylene glycol diglycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, glycerin diglycidyl ether of glycerin diglycidyl ether, (Meth) acrylic acid modified product of bisphenol A diglycidyl ether, a (meth) acrylic acid modified product of bisphenol A diglycidyl ether, a (meth) acrylic acid modified product of bisphenol A diglycidyl ether, (Meth) acrylic acid modified product of ether, propylene oxide modified bisphenol S diglycidyl Le of (meth) acrylic acid modified product, bisphenol F diglycidyl more preferably (meth) acrylic acid modified product of glycidyl ether of (meth) acrylic acid-modified water, and propylene oxide-modified bisphenol F diglycidyl ether. Further, it is also possible to use aliphatic diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (Meth) acrylic acid modified product of glycidyl ether, (meth) acrylic acid modified product of propylene glycol diglycidyl ether, (meth) acrylic acid modified product of tripropylene glycol diglycidyl ether, modified product of glycerin diglycidyl ether (Meth) acrylic acid modified product of bisphenol A diglycidyl ether, (meth) acrylic acid modified product of bisphenol A diglycidyl ether, and (meth) acrylic acid modified product of propylene oxide modified bisphenol A diglycidyl ether.

Methacrylic acid modified product of ethylene glycol diglycidyl ether, acrylic acid modified product of propylene glycol diglycidyl ether, acrylic acid modified product of tripropylene glycol diglycidyl ether, acrylic acid modified product of glycerin diglycidyl ether, Methacrylic acid modified products of bisphenol A diglycidyl ether, acrylic acid modified products of bisphenol A diglycidyl ether, methacrylic acid modified products of propylene oxide modified bisphenol A diglycidyl ether, and propylene oxide modified bisphenol As the acrylic acid modified product of diglycidyl ether A, the following commercially available products can be used.

A specific example of the methacrylic acid-modified product of ethylene glycol diglycidyl ether is epoxy ester 40EM (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of the acrylic acid-modified product of propylene glycol diglycidyl ether is epoxy ester 70PA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of the acrylic acid-modified product of tripropylene glycol diglycidyl ether is epoxy ester 200PA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A concrete example of an acrylic acid-modified product of glycerin diglycidyl ether is an epoxy ester 80 MFA (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified product of bisphenol A diglycidyl ether is epoxy ester 3000MK (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of bisphenol A diglycidyl ether is epoxy ester 3000A (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the methacrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002M (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). A specific example of the acrylic acid-modified product of propylene oxide-modified bisphenol A diglycidyl ether is epoxy ester 3002A (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

1-1-4. Monohydroxy compound

In the present invention, as a material for obtaining the polyester amide acid (A), a monohydroxy compound having no polymerizable double bond and / or a monohydroxy compound having a polymerizable double bond may be used. When the monohydroxy compound is used, the storage stability of the photosensitive composition is improved.

Concrete examples of the monohydroxy compound having no polymerizable double bond are preferably isopropyl alcohol, 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 ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, dimethylbenzylcarbinol, and 4-methoxyphenol (hydroquinone monomethyl ether; MEHQ).

Specific examples of the monohydroxy compound having a polymerizable double bond are preferably furfuryl alcohol, allyl alcohol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl Hydroxypropyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-hydroxy (meth) acrylanilide, 1,4-cyclohexanedimethanol mono Acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (metha) acrylate, (Meth) acrylic acid modified product of phenylglycidyl ether, (meth) acrylic acid modified product of tert-butylphenyl glycidyl ether, and (meth) acrylic acid of another compound containing one epoxy group per molecule Denatured water And at least one of them may be used.

Of these, benzyl alcohol, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, 4-methoxyphenol, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Acrylate such as butyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, Methanol mono (meth) acrylate and 3- (2-hydroxyphenyl) (meth) acrylic acid are more preferred. Compatibility of the polyester amide acid (A) produced by using these components with the epoxy group-containing polymer, the epoxy compound (D), the epoxy curing agent (E) and the inorganic fine particles (F) (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxybutyl (meth) acrylate, and the like. The use of 4-hydroxyphenyl (meth) acrylate, p-hydroxy (meth) acrylanilide and 1,4-cyclohexanedimethanol mono (meth) acrylate is particularly preferred.

Acrylic acid anhydride, 4-hydroxyphenyl methacrylate, p-hydroxy (meth) acryl anilide, and 1,4-cyclohexanedimethanol monoacrylate. A specific example of 4-hydroxyphenyl methacrylate is HQMA (trade name; manufactured by Osaka Organic Chemical Industry Co., Ltd.). A specific example of p-hydroxy (meth) acrylanilide is HMAd (trade name; manufactured by Osaka Organic Chemical Industry Co., Ltd.). A specific example of 1,4-cyclohexanedimethanol monoacrylate is 1,4-cyclohexanedimethanol monoacrylate (CHDMMA) (trade name; Nihon Kasei Co., Ltd.).

The monohydroxy compound is preferably reacted in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyhydric hydroxy compound. More preferably 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

The polyester amide acid (A) used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the above raw materials. By doing so, the residual film ratio of the cured film is improved, which is preferable. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. The molar ratio of styrene / maleic anhydride to the components constituting the styrene / maleic anhydride copolymer is 0.5 to 4, preferably 1 to 3. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names, manufactured by Kawahara Oil Company, Ltd.). Of these, SMA1000P in which the heat resistance and alkali resistance of the cured film are improved is particularly preferable.

The styrene-maleic anhydride copolymer preferably contains 0 to 500 parts by weight per 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride, diamine, and polyhydric hydroxy compound. More preferably 10 to 300 parts by weight.

1-1-6. Silicon-containing monoamines

In the synthesis of the polyester amide acid (A), other raw materials other than those described above may be included as necessary in the range that does not impair the object of the present invention as a raw material, and examples of other raw materials include silicon-containing monoamines .

Specific examples of the silicon-containing monoamines used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- Aminobutyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltrimethoxysilane, p-aminobutyltrimethoxysilane, Aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of them may be used.

Of these, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane which are excellent in the acid resistance of the cured film are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable in view of acid resistance and compatibility.

The silicon-containing monoamine preferably contains 0 to 300 parts by weight, more preferably 5 to 200 parts by weight, per 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride, diamine, and polyhydric hydroxy compound.

1-1-7. The solvent used for the synthesis reaction of the polyester amide acid (A)

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amide acid (A) 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 acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and cyclohexanone. Among these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

1-1-8. Synthesis method of polyester amide acid (A)

In the method for synthesizing the polyester amide acid (A) used in the present invention, X mole of tetracarboxylic dianhydride, Y mole of diamine, and Z mole of polyhydric hydroxy compound are reacted in the solvent. In this case, it is preferable that X, Y, and Z are defined by the ratio in which the relationship of the following formulas (1) and (2) is established between them. When the content is 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, more preferably 1.0? Z / Y? 5.0. In the formula (2), 0.5? (Y + Z) / X? 4.0, and more preferably 0.6? Y + Z / X? 2.0.

The polyester amide acid (A) to be used in the present invention is a polyester amide acid (A) having an acid anhydride group (-CO-O-CO-) at the terminal end thereof under the conditions of excessively using X relative to Y + Is thought to be generated excessively in comparison with molecules having an amino group or hydroxyl group. When the reaction is carried out by such a monomer composition, the above-mentioned monohydroxy compound may be added, if necessary, in order to react with the acid anhydride group at the terminal of the molecule to esterify the terminal. The polyester amide acid (A) obtained by reacting with a monohydroxy compound added improves the compatibility with the epoxy compound (D) and the epoxy curing agent (E), and improves the applicability of the photosensitive composition of the invention containing them do.

In the case of reacting with the above-described monomer composition, a silicon-containing monoamine may be added in order to react with an acid anhydride group at the terminal of the molecule to introduce a silyl group at the terminal. When the photosensitive composition containing the polyester amide acid (A) obtained by adding and reacting the silicon-containing monoamine is used, the acid resistance of the cured film is improved.

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 amount of tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound, because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

The order of addition of the reaction raw materials to the reaction system is not particularly limited. That is, a method of simultaneously adding a tetracarboxylic dianhydride, a diamine, and a polyhydric hydroxy compound to a reaction solvent, a method of dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, followed by adding a tetracarboxylic dianhydride, A method in which a carboxylic acid dianhydride and a polyhydric hydroxy compound are reacted in advance and then a diamine is added to the reaction product or a method in which a tetracarboxylic dianhydride and a diamine are reacted in advance and then a polyhydric hydroxy compound Or a method in which the catalyst is added.

When the above-mentioned silicon-containing monoamine is reacted, after the reaction between the tetracarboxylic acid dianhydride and the diamine and the polyhydric hydroxy compound, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added, Deg.] C for 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

The polyester amide acid (A) thus synthesized 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 acid dianhydride, a diamine, An amino group, a hydroxyl group, a monovalent organic group, or an additive other than these compounds, which is derived from a monocarboxylic acid compound, a hydroxy compound, or a monohydroxy compound. By including such a constitution, the curability is improved.

The weight average molecular weight of the obtained polyester amide acid (A) is preferably 1,000 to 200,000, more preferably 3,000 to 50,000. Within these ranges, flatness and heat resistance are good.

The weight average molecular weight in this specification is the polystyrene reduced value determined by GPC method (column temperature: 35 캜, flow rate: 1 ml / min). PLgel MIXED-D (Agilent Technologies Co., Ltd.) was used as a column, and THF was used as a mobile phase, and polystyrene having a molecular weight of 645 to 132,900 (for example, Polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies Co., Can be measured. The weight average molecular weights of commercially available products in this specification are catalog published values.

1-2. The compound (B) having a polymerizable double bond

1-2-1. A compound having two or more polymerizable double bonds per molecule

The compound (B) having a polymerizable double bond used in the present invention is not particularly limited, but is preferably a compound having two or more polymerizable double bonds per molecule.

The compound (B) having a polymerizable double bond is used in an amount of 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), but preferably 50 to 300 parts by weight.

Examples of the compound having two or more polymerizable double bonds per molecule contained in the photosensitive composition of the present invention include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Acrylate, epichlorohydrin denatured ethylene glycol di (meth) acrylate, epichlorohydrin denatured diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Epichlorohydrin modified diethylene 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 Propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) (Meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (Meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, epichlorohydrin modified trimethylol propane tri (meth) acrylate, ditrimethylol propane Tetra (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate (Meth) acrylate, epichlorohydrin-modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin-modified 1,6-hexanediol di Acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid di (meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol (Meth) acrylate, pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide modified acrylate, pentaerythritol tri ) Acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl-modified dipenta (Meth) acrylate modified with erythritol tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (Meth) acrylate, bis [(meth) acryloxy neopentyl 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 ) Acrylate, 1,3-butylene glycol (meth) acrylate, dicyclopentanyl diacrylate, polyester diacrylate, polyester tree (Meth) acrylate, ethylene tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, ethylene oxide modified di (meth) acrylate, ethylene oxide modified phosphoric tri (meth) acrylate, ethylene oxide modified phosphoric acid Di (meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di Acrylate, isocyanuric acid ethylene oxide-modified triacrylate, caprolactone-modified tris [(meth) acryloxyethyl (meth) acrylate] ] Isocyanurate, (meth) acrylated isocyanurate, phenylglycidyl ether acrylate Hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone (Meta) acrylic acid modified product of a phenol novolak type epoxy resin, a (meth) acrylic acid modified product of a cresol novolak type epoxy resin, a diisocyanate urethane prepolymer, a dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, Acrylic acid-modified products, and carboxylic acid-containing urethane acrylate oligomers.

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

Among the compounds having two or more polymerizable double bonds per molecule, it is preferable to use compounds having two or more polymerizable double bonds per molecule, such as trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, (Meth) acrylate oligomer, isocyanuric acid ethyleneoxide-modified diacrylate, isocyanuric acid ethyleneoxide-modified triacrylate, or a mixture thereof is preferably used from the viewpoints 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 diacryl , Isocyanuric acid ethylene oxide-modified triacrylate, and mixtures thereof, the following commercially available products can be used.

A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name, manufactured by Toa Synthetic Co., Ltd.). Specific examples of mixtures of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M-306 (65-70 wt%), M-305 (55-63 wt%) and M-450 (10 wt% ) (All trade names: Doa Synthetic Co., Ltd., content in the parentheses is the catalog value of the content of pentaerythritol triacrylate in the mixture). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate include Aronix M-403 (50 to 60 wt%), M-400 (40 to 50 wt%), M-402 40% by weight), M-406 (25 to 35% by weight) and M-405 (10 to 20% by weight) The catalog value of the content of dipentaerythritol pentaacrylate in the mixture). Concrete examples of the polybasic acid-modified (meth) acryl oligomer include Aronix M-510 and M-520 (all trade names, Doa Synthetic Co., Ltd.). A specific example of the isocyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name, manufactured by Toa Gosei Co., Ltd.). Specific examples of the mixture of isocyanuric acid ethyleneoxide-modified diacrylate and isocyanuric acid ethyleneoxide-modified triacrylate include Aronix M-315 (3-13% by weight) (trade name: Doa Synthetic Co., Is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture). A specific example of the acrylic acid-modified product of the phenol novolak type epoxy resin is TEA-100 (trade name, manufactured by KSM). A specific example of the acrylic acid-modified product of the cresol novolak type epoxy resin is CNEA-100 (trade name, KSM Co., Ltd.).

1-2-2. Other compounds having a polymerizable double bond

The compound (B) having a polymerizable double bond may contain a compound having another polymerizable double bond which does not correspond to a compound having two or more polymerizable double bonds per molecule. As the other compound having a polymerizable double bond, in the photosensitive composition of the present invention, at least one polymerizable double bond per molecule and one functional group selected from -OH and -COOH May be further contained. The compound having one polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH per molecule is preferably 1 to 50 parts by weight per 100 parts by weight of the polyester amide acid, .

Examples of the compound having one such polymerizable double bond per molecule and having at least one functional group selected from -OH and -COOH per molecule include (meth) acrylic acid, hydroxyethyl (meth) acrylate, (Meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy- Acrylates such as 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 4- (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono 2-hydroxyphenyl) (meth) acrylic acid, and? -Carboxyethyl (meth) acrylate. .

Of these, 4-hydroxyphenyl (meth) acrylate and p-hydroxy (meth) acrylanilide are preferred because of their good resolution.

1-3. The photopolymerization initiator (C)

The photopolymerization initiator (C) contained in the photosensitive composition of the present invention contains a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), and an epoxy curing agent ) And the inorganic fine particles (F), as long as it is capable of initiating polymerization of the composition.

Examples of the photopolymerization initiator (C) contained in the photosensitive composition of the present invention include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, Diethyl thioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 2-methylethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl IRGACURE 907, BASF Japan KK), 2- (dimethylamino) -1- [4- (methylthio) phenyl] -2- (4-morpholinyl) (Trade name: IRGACURE 369, manufactured by BASF Japan KK), ethyl 4-dimethylaminobenzoate, 4-dimethyl-3- Aminobenzoic acid isoamyl, 4,4'-di (t-butylperoxycar 2- (O-phenyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- Propane, 1 - [4- [4- (2-hydroxyphenyl) -1H-pyrazolo [l, (Trade name: ADEKA NCI-930, manufactured by ADEKA), Adeka's NCI-831 (trade name: ADEKA Co., Ltd.), and phenanthio] Trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) - (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis -4,6-bis (trichloromethyl) -s- Triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) (Trichloromethyl) -s-triazine, 1,3-bis (trichloro (meth) acrylate) (4'-methoxyphenyl) -s-triazine, 2- (p-toluenesulfonyl) Dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin) (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis -Tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl Bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis , 2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetra (2-methyl-2-morpholinopropionyl) -9-n (2-methyl-2-dimethylaminopropionyl) carbazole, - dodecyl carbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro -3- (1H- pyrrole -1-yl) -phenyl) titanium, and the like.

The photopolymerization initiator (C) may be used alone, or two or more photopolymerization initiators may be used in combination. Among the photopolymerization initiators (C), α-aminoalkylphenone-based, acylphosphine oxide-based, oximeester-based photopolymerization initiators are preferable from the viewpoints of sensitivity of the coating film upon exposure and transparency of the cured film. In the present specification, a thin film obtained by preliminarily drying (prebaking) 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 a subsequent process such as exposure-development-cleaning-drying, and then becomes a cured film by main firing (post-baking). In the present specification, the thin films in the steps from the preliminary drying to the drying are all referred to as " coating films ", and at any step of the film formation step, for example, Of the coating film.

Among the photopolymerization initiators (C), preferred are 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O- More preferably 20% by weight or more based on the total weight of the photopolymerization initiator from the viewpoints of the sensitivity of the coating film and the transparency of the cured film (hereinafter, referred to as " - (2-hydroxyethoxy) . It is more preferable that the content is 50% by weight or more. Wherein the photopolymerization initiator is at least one selected from the group consisting of 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (O-benzoyloxime) Hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) alone.

1-4. The epoxy compound (D)

The epoxy compound (D) used in the present invention contains 2 to 10 epoxy groups per molecule. By adding the epoxy compound (D) to the photosensitive composition of the present invention, the heat resistance of the cured film can be enhanced. When the epoxy compound (D) is 20 to 200 parts by weight based on 100 parts by weight of the polyester amide acid (A), the flatness is improved.

As a preferable example of the epoxy compound (D), 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celloxide 2021P, (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane (trade name, Celloxide 3000, Daicel Inc.), 2- [4- Bis [4- [1- [4-methoxyphenyl] ethyl] phenyl] Phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2 (2-methylpropoxy) 2- propanediol (trade name: TECHMORE VG3101L, manufactured by PRINTEC), 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [ Ethyl] phenyl] propane, 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether (trade name: jER 1032H60, Mitsubishi Chemical Co., , 1,3-bis (oxirane (1H, 3H, 5H) -triene, 2,2-bis (hydroxymethyl) -1- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol (trade name: EHPE3150, Daicel Co., Ltd.).

1-5. Epoxy curing agent (E)

In the photosensitive composition of the present invention, an epoxy curing agent (E) is used to improve flatness and chemical resistance. Examples of the epoxy curing agent (E) include an acid anhydride type curing agent, an amine type curing agent, a phenol type curing agent, an imidazole type curing agent, a catalyst type curing agent and a thermosensitive acid generator such as a sulfonium salt, a benzothiazonium salt, an ammonium salt and a phosphonium salt Etc. From the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film, an acid anhydride-based curing agent or an imidazole-based curing agent is preferable.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid anhydride, and hexahydrotrimellitic anhydride, And polycarboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride. Among them, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride which can improve the heat resistance of the cured film without deteriorating the solubility of the photosensitive composition in a solvent are particularly preferable.

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

1-6. The inorganic fine particles (F)

The inorganic fine particles (F) are not particularly limited, and the inorganic fine particles (F) are preferably selected from the group consisting of Si, Al, Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, , Y, Zr, Nb, Mo, Tc, Ru, Ag, In, Sn, Sb, Te, Cs, Ba, Hf, Ta, W, Re, La, Ce, Pr, Nd, (MgAl ₂ O ₄ ) such as oxides, sulfates, carbonates and fluorides of Tb, Dy, Ho, Er, Tm, Yb and Lu.

Among them, the inorganic fine particles (F) are preferably oxide particles of the Group 4 elements of the periodic table, and the refractive index of the resulting cured film can be further increased by adding fine particles having a high refractive index. Specific examples thereof include composite particles of titanium oxide, zirconium oxide, hafnium oxide and metal oxides thereof, and silicon oxide and tin oxide. From the viewpoint of enhancing the refractive index of the resulting cured film, titanium oxide and zirconium oxide desirable.

Since titanium oxide has photocatalytic activity, it is preferable to coat the surface of the particles with silicon oxide for use in optical applications. In addition, anatase type and rutile type exist in titanium oxide due to difference in crystal form, but rutile type is preferable because of high refractive index and excellent light resistance.

When light enters a composition in which the inorganic fine particles (F) are dispersed in the photosensitive composition, Rayleigh scattering occurs due to dispersed particles. However, when the Rayleigh scattering is reduced, the irradiated light can transmit through the composition without scattering. For example, when the composition is cured to produce an encapsulant or the like of an electronic device, the light extraction efficiency as described above can be improved. Further, when the optical waveguide is made by curing the composition, scattering of the optical signal propagating through the optical waveguide is small, so that the light propagation loss of the optical waveguide is reduced. It is preferable that the primary particle diameter of the inorganic fine particles (F) in the composition is small in order to suppress the scattering because the Rayleigh scattering is proportional to the third power of the particle diameter of the dispersed particles.

The primary particle diameter of the inorganic fine particles (F) in the photosensitive composition is 1 nm or more to prevent whitening of the cured film due to secondary agglomeration of the inorganic fine particles (F), and is 100 nm or less for excellent surface uniformity in forming a thin film . The primary particle size is preferably 1 to 50 nm, more preferably 5 to 15 nm. The inorganic fine particles (F) in the composition are present in the primary particle state in which aggregation is completely released and in the state in which a plurality of primary particles are aggregated. Here, the primary particle diameter of the inorganic fine particles (F) is the particle diameter of the non-aggregated particles, and the aggregated particle diameter of the primary aggregated particles is the aggregated particle diameter. Examples of the method for measuring the primary particle size of the inorganic fine particles (F) in the composition include a method of directly observing the particles by SEM (scanning electron microscope) or TEM (transmission electron microscope) Method.

The refractive index (refractive index nD as a bulk material instead of nano particles) of the inorganic fine particles (F) is 1.6 to 3.5, preferably 1.8 to 3.0, and more preferably 2.0 to 2.8.

The inorganic fine particles (F) may be in powder form or may be a solvent dispersion. Examples of the dispersion medium include methanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrolidone and propylene glycol monomethyl ether.

Examples of commercially available products that can be used as the inorganic fine particles (F) include titanium oxide nanopillar dispersion (ND-139 manufactured by Teika Co., Ltd., C007M manufactured by Mikuni Color Company), zirconium oxide nanopillar dispersion (manufactured by Mikuni Color Company (Manufactured by Shin-Etsu Chemical Co., Ltd., MHI B642M, manufactured by Mikuni Color Co., Ltd., B943M, manufactured by Solar Corporation), silicon oxide-coated anatase titanium oxide- (TS series), and zirconium oxide-methyl ethyl ketone dispersion sol (HXU-120JC, manufactured by Osaka Cement Co., Ltd.), and the like.

The content of the inorganic fine particles (F) is 30 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A). The content of the inorganic fine particles (F) is 30 parts by weight or more so that the refractive index of the resulting cured product is in the below-mentioned desired range. In addition, when the pattern processing by the photolithography method is carried out, the content of the inorganic fine particles (F) is preferably not more than 400 parts by weight in order that the residual film ratio of the resulting cured product is proper.

The refractive index (nD) when the photosensitive composition is a cured film is 1.6 to 3.0. Preferably 1.6 to 2.0, and more preferably 1.6 to 1.8. The refractive index (nD) is the refractive index for the D-line of sodium and the wavelength of 589.3 nm, and the measurement method is as shown in the examples.

1-7. Other components

To the photosensitive composition of the present invention, various additives may be added to improve coating uniformity, adhesiveness, transparency, resolution, flatness, and chemical resistance. Examples of the additives include antioxidants such as anionic, cationic, nonionic, fluorinated or silicone surfactants, coupling agents, hindered phenol-based, hindered amine-based, phosphorus-based and sulfur-based compounds, molecular weight regulators, ultraviolet absorbers, An antioxidant, an antioxidant, a heat-crosslinking agent, a photoacid generator and a solvent.

1-7-1. Surfactants

In the photosensitive composition of the present invention, a surfactant may be added in order to improve coating uniformity. Specific examples of the surfactant include polyphosphoric acid esters such as polyphosphoric acid esters. 75, Polyflow No. " 90, poly flow No. Disperbyk 161, Disperobic 162, Disperobic 163, Disperobic 164, Disperobic 166, Disperobic 170, Disperobic 180, Disperobic 181, Disperbyk 182 (all trade names, , BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK- (Trade name: Shin-Etsu Chemical Co., Ltd.), Surflon S611 (trade name, available from AGC Seiyam Chemical Co., Ltd.), Futagent 222F, Futagent 208G 430, Megapack F-430, Megaplock F-430, Megaplock F-430, Megaplock F-430, Megaplock F-480, F-554, Megaplock F-555, Megaplock F-554, Megaplock F-554, Megaplock F-474, Megaplock F- 556, MegaPak F-558, MegaPak F TEGO Twin 4000, TEGO Twin (manufactured by DIC Corporation), Megapak RS-75, Megapak RS-75, Megapak RS- 4100, TEGO Flow 370, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N (all trade names, Ebonic Japan Co., Ltd.), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkylpolyoxyethylene ethers, (Fluoroalkylpolyoxyethylene ether), a fluoroalkyltrimethylammonium salt, a fluoroalkylaminosulfonate salt, a polyoxyethylene nonylphenyl (meth) acrylate, a fluoroalkylsulfonate salt, Ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan monostearate, sorbitan monostearate, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl And diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

Of these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-368, Surfron S611, Putagent 710FL, Putagent 710FM, Putagent 710FS, Putagent 601AD, Putagent 650A, Examples of the fluoroalkylbenzene sulfonic acid salts include fluorocarbonsulfonic acid salts such as Parkfaque F-477, Megafac F-556, Megafac F-559, Megapak RS-72-K, Megapak DS- 21, TEGO Twin 4000, At least one selected from the group consisting of fluoroalkyl ethers, fluoroalkyl ethers, fluoroalkylsulfonates, fluoroalkyltrimethylammonium salts and fluoroalkylaminosulfonates is preferred because the coating uniformity of the photosensitive composition is enhanced.

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

1-7-2. Coupling agent

The photosensitive composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples thereof include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Saira S510 , JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (trade name: Saira S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane Silane coupling agents such as a polymer of 3-glycidyloxypropyltrimethoxysilane (for example, trade name: COATOSIL MP 200, Momentive Performance Material Joint-Stock Co., Ltd.) An aluminum-based coupling agent such as an aliphatic hydrocarbon-based coupling agent, an aliphatic hydrocarbon-based coupling agent, and an alkoxy aluminum diisopropylate; and a titanate-based coupling agent such as tetraisopropyl bis (dioctylphosphite) titanate.

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

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

1-7-3. Antioxidant

The photosensitive composition of the present invention may further contain an antioxidant in order to improve transparency and prevent yellowing when the cured film is exposed to high temperatures.

To the photosensitive composition of the present invention, an antioxidant such as a hindered phenol-based, hindered amine-based, phosphorus-based, or sulfur-based compound may be added. Among them, the hindered phenol system is preferable from the viewpoint of weather resistance. Specific examples include Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, Irganox 1076, Irganox 1076FD, Irganox 1098, Irganox 1135, Irganox 1330, Irganox 1726, Irganox 1425WL, Irganox 1520L, Irganox 245, Irganox 245FF, Irganox 259, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-80 (all trade names, ADEKA Co., Ltd.), Irganox 3114, Irganox 565 (all trade names; BASF Japan Co., . Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

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

1-7-4. Molecular weight regulator

The photosensitive composition of the present invention may further contain a molecular weight regulator in order to suppress the increase in molecular weight by polymerization and to exhibit excellent resolution. Examples of the molecular weight adjusting agent include mercaptans, xanthogens, quinones, hydroquinones, phenols, catechol, cresols, 2,4-diphenyl-4-methyl-1-pentene and phenothiazine .

Specific examples of the molecular weight regulator include 1,4-naphthoquinone, 1,2-benzoquinone, 1,4-benzoquinone, methyl-p-benzoquinone, anthraquinone, hydroquinone, methylhydroquinone, Di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,4-dihydroxynaphthalene, 3,6-dihydroxybenzonorboranes, 4-methoxyphenol, 2 , 2 ', 6,6'-tetra-t-butyl-4,4'-dihydroxybiphenyl, stearyl 3- (3,5-di-t- butyl-4-hydroxyphenyl) , 2'-methylenebis (6-t-butyl-4-ethylphenol), 2,4,6-tris (3 ', 5'-di- 4-hydroxyphenyl) propionate], 4-t-butyl pyrocatechol, n-hexyl mercaptan, n-octyl mercaptan, n Dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,6-di-t-butyl- -Butylidenebis (6-t-butyl-m- Cresol), 2,4-diphenyl-4-methyl-1-pentene, phenothiazine, 2-hydroxy- Naphthoquinone, and the like.

1-7-5. Ultraviolet absorber

The photosensitive composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the deterioration preventing ability of the patterned transparent film formed.

Specific examples of ultraviolet absorbers are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, TINUVIN 765 (both trade names; BASF Japan Co., Ltd.).

The ultraviolet absorber is used in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-7-6. Anti-aggregation agent

The photosensitive composition of the present invention may contain an anti-aggregation agent from the viewpoint of mixing the solid content with a solvent to prevent agglomeration.

Specific examples of the coagulation inhibitor include Disperbyk-145, Disperby-161, Disperby-162, Disperby-163, Disperby-164, Disperby-182, Disperby-184, Disperby- Disperbyk-2163, Disperbyk-2164, BYK-220S, Disperbyk-191, Disperbyk-199, Disperbyk-2015 (all trade names; Big Chem Japan Co., Ltd.), FTX-218, (All trade names; Neos Co., Ltd.), FLOREN G-600 and FLOWREN G-700 (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.).

The coagulation inhibitor is added in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-7-7. Thermal crosslinking agent

The photosensitive composition of the present invention may contain a heat crosslinking agent in view of further improving heat resistance, chemical resistance, uniformity in film plane, flexibility, flexibility and elasticity.

Specific examples of thermal crosslinking agents include NIKARAK MW-30HM, NIKARAK MW-100LM, NIKARAK MX-270, NIKARAK MX-280, NIKARAK MX-290, NIKARAK MW-390, Sanwa Chemical Co., Ltd.).

The heat crosslinking agent is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

1-7-8. Photoacid generator

The photosensitive composition of the present invention may contain a photoacid generator from the viewpoint of improving the resolution. As the photoacid generator, a 1,2-quinonediazide compound is used.

Specific examples of the 1,2-quinonediazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzo 2-naphthoquinonediazide-5-sulfonic acid ester, 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-naphthoquinonediazide-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) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane- (P-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri -Naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- (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;

(2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Methylphenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4'- [1- [4- [1- [4- hydroxyphenyl] , 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- ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,6,7,5', 6 ', 7'-hexanol-l, 2-naphthoquinonediazide- Sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,6,7,5', 6 ', 7'-hexanol- Toquinonediazide-5-sulfonic acid ester;

2,2,4-trimethyl-7,2 ', 4'-trihydroxyflagane-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,2,4-trimethyl- , 4'-trihydroxyplazane-1,2-naphthoquinonediazide-5-sulfonic acid ester.

The photoacid generator is added in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

1-8. 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 the polyester amide acid (A), the compound having a polymerizable double bond (B), the photopolymerization initiator (C), the epoxy compound (D) Do. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, Methoxypropionate, methyl 3-hydroxypropionate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methoxypropionate, methyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, Propyleneglycol monomethyl ether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, propyleneglycol monomethylether, Propylene glycol monomethyl ether acetate, 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 glycol monoethyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl Ether. The solvent may be one of these, or a mixture of two or more of them.

2. Preservation of photosensitive compositions

When the photosensitive composition of the present invention is stored at a temperature in the range of -30 占 폚 to 25 占 폚, stability with time of the composition becomes favorable. If the storage temperature is -20 占 폚 to 10 占 폚, no precipitates are more preferable.

3. The cured film obtained from the photosensitive composition

The photosensitive composition of the present invention comprises a mixture of a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), an epoxy curing agent (E) And optionally adding and optionally adding a solvent, a coupling agent, a surfactant, and other additives according to the desired properties, and mixing and dissolving them uniformly.

When the photosensitive composition prepared as described above (after dissolving in a solvent in a solid state without solvent) is applied to the base surface and the solvent is removed, for example, by heating, a coating film can be formed. The application of the photosensitive composition to the surface of the substrate can be carried out by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexo printing method, a spraying method, and a slit coating method. Subsequently, this coating film is heated (prebaked) on a hot plate, an oven or the like. The heating conditions differ depending on the kind of each component and the blending ratio, but it is usually from 70 to 150 DEG C for 5 to 15 minutes in an oven and from 1 to 5 minutes in a hot plate.

Thereafter, the coating film is irradiated with ultraviolet rays through a mask of a desired pattern shape. The amount of ultraviolet radiation is suitably 5 to 1000 mJ / cm 2 by i-line. The photosensitive composition to which ultraviolet light is irradiated becomes a three-dimensional crosslinked product by polymerization of the compound (B) having a polymerizable double bond, and is insoluble in an alkali developing solution.

Subsequently, the coating film is immersed in an alkali developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon, or the like, and an unnecessary portion is dissolved and removed. Specific examples of the alkali developing solution 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. In addition, an appropriate amount of methanol, ethanol, and a surfactant may be added to the alkali developing solution.

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

The cured film thus obtained is further subjected to a heat treatment at the time of heating in such a manner that 1) the polyamic acid portion of the polyester amide acid (A) is dehydrated and cyclized to form an imide bond, and 2) Since the carboxylic acid reacts with the epoxy group-containing polymer to have a high molecular weight, it is very strong and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance and sputter resistance. Further, this cured film has a good residual film ratio after development. 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 pickup element can be manufactured by using this color filter. In addition to the protective film for the color filter, the cured film of the present invention is also effective as a protective film for a transparent insulating film formed between the TFT and the transparent electrode, a transparent insulating film formed between the transparent electrode and the orientation film, and an LED luminous body. Further, the cured film of the present invention has a high refractive index and is also effective as an optical waveguide for an organic EL device.

The electronic device of the present invention is an electronic device having the above-mentioned cured film-attached substrate. By using the substrate with a cured film of the present invention, a flexible electronic device can be obtained.

Since the cured product obtained from the photosensitive composition of the present invention has a high refractive index, it is preferably used for an optical waveguide. The optical waveguide is formed on a circuit substrate such as an electronic apparatus and has an action of transmitting an optical signal between ICs mounted on the substrate. The optical waveguide is composed of a core portion in which an optical signal propagates and a cladding portion having a refractive index lower than that of the core portion surrounding the core portion. The optical waveguide includes a channel type optical waveguide having a structure in which a cladding portion surrounds a linear core portion and a slab type optical waveguide having a structure in which a cladding portion in a layer shape is covered above and below the core portion in a layer form. Can be used either in the core portion or in the cladding portion, or in either one of the core portion and the cladding portion.

The refractive index and thickness of the cladding portion and the core portion of the optical waveguide can be arbitrarily selected depending on the optical waveguide to be designed. In the case of a multimode optical waveguide, it is preferable to increase the refractive index difference between the core portion and the cladding portion to thicken the core portion. In the case of the single mode optical waveguide, the refractive index difference between the core portion and the cladding portion is reduced, and the core portion is made thinner, so that the single mode propagation is realized.

Example

Next, the present invention will be described concretely with reference to Synthesis Examples, Reference Examples, Examples, and Comparative Examples, but the present invention is not limited at all by these Examples.

With respect to abbreviations of the components in Tables 1 and 2,

ODPA is a 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride,

BT-100 is a 1,2,3,4-butanetetracarboxylic dianhydride,

SMA1000P is a copolymer of styrene-maleic anhydride copolymer (trade name: Kawahara Yuka Co., Ltd.)

MEHQ is 4-methoxyphenol (hydroquinone monomethyl ether),

Epoxy ester 70PA is an acrylic acid-modified product of propylene glycol diglycidyl ether (trade name, manufactured by Kyoeisha Chemical Co., Ltd.)

DDS is 3,3'-diaminodiphenyl sulfone,

M-520 is a compound having a polymerizable double bond Aronix M-520 (trade name: Doa Synthetic Co., Ltd.)

NCI-930 is a photopolymerization initiator, Adekaques NCI-930 (trade name: ADEKA Co., Ltd.)

VG3101L is an epoxy compound TECHMORE VG3101L (trade name: PRINTEC Co., Ltd.)

TMA is an epoxy curing agent, trimellitic anhydride,

ND-139 is an inorganic fine particle (trade name: Teika Co., Ltd.)

S510 is a coupling agent, Ace S510 (trade name, JNC Co., Ltd.)

AO-60 is an antioxidant ADK STAB AO-60 (trade name: ADEKA)

BYK-342 is a surfactant, BYK-342 (trade name; Big-Chem Japan Co., Ltd.)

PGMEA is a solvent comprising propylene glycol monomethyl ether acetate,

PGME is a solvent comprising propylene glycol monomethyl ether,

EDM is a solvent diethylene glycol ethyl methyl ether.

[Synthesis Example 1] Synthesis of polyester amide acid (A1) solution

Into a four-necked flask equipped with a stirrer was added dehydrated and purified PGMEA, BT-100, SMA1000P, benzyl alcohol and 1,4-butanediol in the following proportions in that order, followed by stirring at 125 DEG C for 3 hours in a dry nitrogen stream.

PGMEA 42.81 g

BT-100 3.04 g

SMA1000P 14.45 g

Benzyl alcohol 4.64 g

0.92 g of 1,4-butanediol

Thereafter, the reaction solution was cooled to 25 DEG C, DDS and PGMEA were added in the following weights, and the mixture was stirred at 20 to 30 DEG C for 2 hours and then at 125 DEG C for 2 hours.

DDS 0.95g

PGMEA 7.04 g

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

Thereafter, the reaction solution was cooled to 25 deg. C, trimellitic anhydride (TMA) and PGMEA were added at the following weights, and the mixture was stirred at 20 to 30 DEG C for 2 hours.

TMA 0.24 g

PGMEA 6.15g

The solution was cooled to room temperature to obtain a 30 wt% solution of light yellow transparent polyester amide acid (A1). A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). The polyester amide acid (A1) thus obtained had a weight average molecular weight of 15,000.

[Synthesis Examples 2 to 4] Synthesis of polyester amide acid (A2 to A4) solutions

Each component was reacted at the temperature, time and ratio (unit: g) shown in Table 1 in accordance with the method of Synthesis Example 1 to obtain a polyester amide acid solution.

[Example 1]

A 30 wt% solution of the polyester amide acid (A1) obtained in Synthesis Example 1, M-520, NCI-930, VG3101L, TMA, ND-139, 2-hydroxy-1,4-naphthoquinone, S510, AO -60, BYK-342, PGMEA, PGME and EDM were mixed and dissolved in the ratio (unit: g) shown in Table 2 and filtered through a membrane filter (0.2 탆) to obtain a photosensitive composition.

[Examples 2 to 8 and Comparative Examples 1 to 2]

Each component was mixed and dissolved in the ratio shown in Table 2 (unit: g) in accordance with the method of Example 1 to obtain a photosensitive composition.

[Film forming method for evaluation]

The photosensitive composition was spin-coated on a glass substrate at 400 rpm for 10 seconds and prebaked on a hot plate at 100 캜 for 120 seconds. Then, using a proximity exposure apparatus TME-150 PRC, exposure was carried out with an exposure gap of 100 mu m through a mask having holes and line patterns of 50 mu m in width in the air. The amount of exposure was measured to 30 mJ / cm 2 by measuring with a cumulative photometer UIT-102 and a UV detector UVD-365 PD. After the exposure, the coated film was subjected to paddle development at 27 DEG C for 60 seconds using a buffer solution of sodium carbonate / sodium hydrogencarbonate, and then the unexposed portion was removed. The developed coating film was washed with pure water for 20 seconds and then dried with a hot plate at 100 DEG C for 2 minutes. Further, post-baking was performed in an oven at 230 캜 for 30 minutes to obtain a glass substrate with a patterned cured film having a thickness of 1.5 탆.

The properties of the cured film thus obtained were evaluated for the residual film ratio, resolution, refractive index, transparency and flatness.

[Evaluation method of residual film ratio]

The film thickness before development and the film thickness after development were measured using a step, surface roughness and fine shape measuring device (trade name: P-17, KLA TENCOR Co., Ltd.), and the residual film ratio (film thickness after development x 100 / Thickness) was calculated. The case where the residual film ratio was 80% or more was evaluated as & cir &, and the case where the residual film ratio after development was less than 80% was evaluated as & cir &

[Evaluation method of resolution]

The resulting glass substrate with a patterned cured film was observed with a 50x optical microscope to evaluate the resolution of holes and line patterns corresponding to a mask size of 50 占 퐉 width. The case where the hole and line pattern were resolved was evaluated as " ", and the case where the resolution was not evaluated was evaluated as " x ".

[Evaluation method of refractive index]

The refractive index of the cured film was measured using a reflective spectroscopic film sublayer FE-3000 (manufactured by Otsuka Electronics Co., Ltd.). The case where the refractive index was 1.60 or more was evaluated as & cir &

[Evaluation method of transparency]

The total light transmittance and haze of the cured film were measured using a haze meter HAZE-GARD PLUS (manufactured by BYK Corporation). A case where the transmittance was 90% or more was evaluated as & cir & and a case where the transmittance was less than 90% was evaluated as & A case where the haze was 1% or less was evaluated as & cir & and a case where the haze was more than 1% was evaluated as x.

[Evaluation method of flatness]

The photosensitive composition was spin-coated at 400 rpm for 10 seconds on the uncured film color filter substrate having pixels including R, G, and B, and prebaked on a hot plate at 100 캜 for 120 seconds. Subsequently, post-baking was performed in an oven at 230 캜 for 30 minutes to obtain a color filter substrate with a cured film having an average film thickness of 1.5 탆 as a protective film. Thereafter, the obtained surface roughness of the color filter substrate with a cured film was measured using a step, surface roughness and fine shape measuring device, and the results are shown in Table 3. When the maximum step difference was 0.25 占 퐉 or less, the flatness was evaluated as?, And when the step was 0.26 占 퐉 or more, the flatness was evaluated as 占. The uncured film color filter substrate used had a maximum step difference of 1 占 퐉.

The evaluation results of the cured films of Examples 1 to 8 and Comparative Examples 1 and 2 are shown in Table 3 below.

As is clear from the results shown in Table 3, it was found that the cured films of Examples 1 to 8 were balanced in all aspects of the film residual rate, resolution, refractive index, transparency and flatness. On the other hand, the cured films of Comparative Examples 1 and 2 do not become "? &Quot; The cured film of Comparative Example 1 had a low residual film ratio, and the cured film of Comparative Example 2 was completely dissolved after development. As described above, when the ratio of the amount of the inorganic fine particles added was within the range of the present invention, all the characteristics could be satisfied by using the polyester amide acid described in Synthesis Example.

The photosensitive composition of the present invention is based on a polyester amide acid having a high heat resistance. The cured film formed from the composition has excellent heat resistance, transparency and flatness, and is superior in the resolution, residual film ratio and refractive index . The cured film of the present invention has excellent properties as an optical material and is used as a protective film for various optical materials such as a color filter, an LED light emitting element and a light receiving element, and as a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the orientation film .

Claims (13)

1. A photosensitive composition comprising a polyester amide acid (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), an epoxy compound (D), an epoxy curing agent (E), and an inorganic fine particle (F);
The polyester amide acid (A) is obtained by reacting X mole of tetracarboxylic dianhydride, Y mole of diamine and Z mole of polyhydric hydroxy compound at a ratio satisfying the relations of the following formulas (1) and (2) And includes a constituent unit represented by the following formula (3) and a constituent unit represented by the following formula (4);
The compound (B) having a polymerizable double bond has two or more polymerizable double bonds per molecule;
The epoxy compound (D) contains 2 to 10 epoxy groups per molecule;
The total amount of the polymerizable double bond-containing compound (B) is 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), the total amount of the epoxy compound (D) is 20 to 200 parts by weight, Composition:
0.2? Z / Y? 8.0 (1)
0.2? (Y + Z) /X? 5.0 (2)

In the formulas (3) and (4), R ¹ is a residue excluding two -CO-O-CO- from a tetracarboxylic acid dianhydride, R ² is a residue excluding two -NH ₂ from a diamine, , And R < ³ > is a residue excluding two -OH from the polyhydric hydroxy compound. The method according to claim 1,
Wherein the raw material component of the polyester amide acid (A) further comprises a monohydroxy compound. 3. The method of claim 2,
Wherein the monohydroxy compound is selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, 3-ethyl-3-hydroxymethyloxetane, and 4-methoxyphenol Lt; / RTI > 4. The method according to any one of claims 1 to 3,
The weight average molecular weight of the polyester amide acid (A) is 1,000 to 200,000;
Wherein the tetracarboxylic acid dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, (Dihydrocarbodiimide) is selected from 2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis Is at least one;
The diamine is at least one selected from 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone;
Wherein the polyhydric hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, and isocyanuric acid tris (2-hydroxyethyl);
Wherein the polymerizable double bond-containing compound (B) is at least one compound selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and isocyanuric acid ethyleneoxide- At least one selected is contained in an amount of 50% by weight or more based on the total weight of the compound having a polymerizable double bond;
Wherein the epoxy compound (D) is at least one selected from the group consisting of 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-methyl- Ethyl] phenyl] phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) ] Propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenoxy] phenyl] ethyl] phenoxy] -2-propanol, 2- [4- (2,3- Tris (4-hydroxyphenyl) ethane triglycidyl ether, 1,3-bis (oxiranylmethyl) propane, (1H, 3H, 5H) -triene, and 2,2-bis (hydroxymethyl) -1- (2-oxiranyl) cyclohexane adduct of 1,3-butanediol and 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of butanol. 5. The method according to any one of claims 1 to 4,
Wherein the photopolymerization initiator (C) is at least one selected from an? -Aminoalkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator. 6. The method according to any one of claims 1 to 5,
Wherein the epoxy curing agent (E) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole. 7. The method according to any one of claims 1 to 6,
The tetracarboxylic acid 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 polyhydric hydroxy compound is 1,4-butanediol;
The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;
The photopolymerization initiator (C) contains a compound represented by the following formula (5) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator;
Wherein the epoxy compound (D) is at least one selected from the group consisting of 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- ] Phenyl] propane, and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- Phenoxy] phenyl] -2- [4- [1, 2-dihydroxyphenyl] Bis [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] propane;
Wherein the epoxy curing agent (E) comprises at least one selected from trimellitic anhydride and 2-undecylimidazole;
Further, a photosensitive composition containing at least one selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent:

Wherein R ⁴ , R ⁵ and R ⁷ are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, R ⁶ is an alkyl group having 1 to 15 carbon atoms, An alkenyl group having 2 to 15 carbon atoms or an alkynyl group having 2 to 15 carbon atoms, and each n is independently an integer of 0 to 5. 8. The method according to any one of claims 1 to 7,
Wherein the raw material of the polyester amide acid (A) comprises a styrene-maleic anhydride copolymer. 9. The method according to any one of claims 1 to 8,
Wherein the inorganic fine particles (F) contain 30 to 300 parts by weight per 100 parts by weight of the polyester amide acid (A). 10. The method according to any one of claims 1 to 9,
The inorganic fine particles (F) are titanium oxide or zirconia having a primary particle diameter of 1 to 100 nm. A cured film obtained from the photosensitive composition according to any one of claims 1 to 10. A color filter having the cured film of claim 11 as a transparent protective film. An electronic device having the cured film of claim 11.