KR20180110582A - Photosensitive compositions - Google Patents

Abstract

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

Description

[0001] PHOTOSENSITIVE COMPOSITIONS [0002]

The present invention relates to a photosensitive material for use in the formation of an insulating material in an electronic part, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, an interlayer insulating film in a display element, ≪ / RTI > Further, the present invention relates to a transparent film formed using the photosensitive composition, and an electronic component having the film.

In the manufacturing process of a device such as a display device typified by a flat panel display, various chemicals such as an organic solvent, an acid, and an alkali solution are processed, or when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature . Therefore, a surface protective film may be formed for the purpose of preventing deterioration, damage and alteration of the surface of the device. These protective films are required to have various properties capable of enduring various treatments in the above-described manufacturing process. Specifically, it is required to have transparency, flatness, light resistance, resistance to chemicals, water resistance, adhesiveness to a base substrate such as glass, and further, chemical resistance such as heat resistance, solvent resistance, acid resistance and alkali resistance.

In recent years, the demand for touch panels has been increasingly thinner and lighter. As a result, it has become possible to provide various characteristics such as adhesiveness to substrates, transparency, flatness, heat resistance, and the like, It is required to be developable that it can be accurately formed. Further, when the manufacturing process of depositing ITO on the insulating film and partially etching the electrode to form an electrode is performed once or several times, resistance to the ITO etchant is also required.

The types of the curable composition for forming these protective films and insulating films are roughly classified into photosensitive compositions and thermosetting compositions. Since the thermosetting composition is completely cured by high-temperature heating at the time of film formation, even if it is heated at a high temperature in subsequent steps, volatile matter generated is small, and heat resistance is excellent. As a thermosetting protective film material having such excellent properties, there is a polyester amide acid composition (for example, see Patent Document 1). However, the scribing line can not be formed in the thermosetting composition, and a large amount of fine residue of the protective film is generated at the time of dividing the production panel, so that a highly advanced panel cleaning process is required afterwards.

On the other hand, the photosensitive composition is composed of a polymer, an 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. Since the photosensitive composition can easily form a scribe line to be used at the time of dividing the production panel, for example, there is an advantage that no fine residue of the protective film is generated, whereas a protective film formed by a conventional photosensitive composition is a thermosetting composition The heat resistance is insufficient.

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

As a photosensitive composition capable of forming a protective film having excellent heat resistance, there are a polyimide precursor composition (see, for example, Patent Document 2) and a soluble polyimide composition (see, for example, Patent Document 3). However, in any of the photosensitive compositions, the organic solvent capable of dissolving the polyimide precursor composition or the soluble polyimide composition to be obtained is limited, and an organic solvent having a very high polarity is required.

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

When these photosensitive compositions are used particularly as a protective film for color filters, if the organic solvents having high polarity are contained, the base color filter layer is immersed and coloring materials such as pigments or dyes contained in the pixels are eluted, It becomes difficult to manufacture a high-quality display device.

Patent Documents 4 and 5 disclose that a photosensitive composition is used as a protective film for a color filter. However, as a result of the inventors attempting to form a protective film using the photosensitive composition described above, the pattern formed is not satisfactory enough , Further improvement is required.

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

In addition, regardless of the photosensitive composition or the thermosetting composition, it is required that these curable compositions have excellent applicability to the base substrate.

Japanese Laid-Open Patent Publication No. 2008-156546 Japanese Patent Application Laid-Open No. 59-068332 Japanese Patent Application Laid-Open No. 2002-003516 Japanese Laid-Open Patent Publication No. 2011-090275 Japanese Laid-Open Patent Publication No. 2016-103010

The object of the present invention is to provide a photosensitive composition which does not require an organic solvent having a high polarity and which gives a cured film excellent in transparency, heat resistance, flatness, resolution and chemical resistance. It is another object of the present invention to provide a cured film formed by the photosensitive composition, and further to provide an electronic component having the cured film.

As a result of intensive studies for solving the above problems, the present inventors have found that a polyester amide acid obtained from the reaction of a compound containing a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound, a compound having a polymerizable double bond, , A composition comprising an epoxy compound, an epoxy curing agent and a molecular weight modifier, and a cured film obtained by curing the composition, thereby accomplishing the present invention.

The present invention includes the following configuration.

(1) A photopolymerizable composition comprising a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), a polymer (D) having an epoxy group, an epoxy compound (E), an epoxy curing agent As the photosensitive composition comprising the modifier (G);

The polyester amide acid (A) is obtained by reacting X mole of a tetracarboxylic dianhydride, Y mole of a diamine and Z mole of a polyhydric hydroxy compound at a ratio in which the relationship of the following formulas (1) and (2) (3) and a constituent unit represented by the following formula (4): " (1) "

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

The polymer (D) having an epoxy group has a weight average molecular weight of 3,000 to 50,000;

The epoxy compound (E) contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000;

The total amount of the 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 polymer (D) having the epoxy group and the epoxy compound (E) Is 20 to 200 parts by weight;

Wherein the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier (G).

0.2? Z / Y? 8.0 (1)

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

In 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 further comprises a monohydroxy compound.

[3] The process 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 and 3-ethyl- The photosensitive composition according to [2].

[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 Or more;

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, isocyanuric acid ethyleneoxide- Modified (meth) acryl oligomer in an amount of 50% by weight or more based on the total weight of the compound having a polymerizable double bond;

The photopolymerization initiator (C) is at least one selected from an? -Aminoalkylphenone-based, acylphosphine oxide-based, oximeester-based photopolymerization initiator;

Wherein the polymer (D) having an epoxy group has an epoxy group which is a reaction product from a mixture of a radically polymerizable monomer (d1) having an epoxy group and a radically polymerizable monomer (d2) other than the above (d1); And,

The photosensitive composition according to any one of [1] to [3], wherein the epoxy curing agent (F) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride and 2-undecylimidazole.

[5] The method according to any one of [1] to [5], wherein the radically polymerizable monomer (d1) having an epoxy group is selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl And at least one selected from diesters;

The photosensitive composition according to [4], wherein the radically polymerizable monomer (d2) other than (d1) comprises at least one bifunctional (meth) acrylate.

[6] The composition according to any one of [1] to [5], wherein the molecular weight modifier (G) is at least one selected from mercaptans, xanthogens, quinones, hydroquinones, Wherein the photosensitive composition is a photosensitive composition.

[7] The process according to [1], wherein the tetracarboxylic dianhydride is selected from 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride More than species;

The diamine is 3,3'-diaminodiphenylsulfone;

The polyhydric hydroxy compound is 1,4-butanediol;

The monohydroxy compound is benzyl alcohol;

The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and polybasic acid modified (meth) acrylic oligomer;

Wherein the bifunctional (meth) acrylate is selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) (Meth) acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate;

Wherein the photopolymerization initiator (C) is at least one selected from the group consisting of 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ -Methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime), and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) ] Phenyl] -2- (O-acetyloxime) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator (C);

Wherein the epoxy curing agent (F) is at least one selected from trimellitic anhydride and 2-undecylimidazole; And,

The photosensitive composition according to [5], further comprising at least one solvent selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent.

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

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

[10] A color filter having the cured film described in [9] as a transparent protective film.

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

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

[13] A transparent insulating film formed between a TFT and a transparent electrode, comprising a cured film according to [9].

[14] A transparent insulating film formed between a TFT and an orientation film, which uses the cured film according to [9].

[15] An LED light source using the cured film according to [9] as a protective film.

[16] An interlayer insulating film having the cured film described in [9] as a transparent protective film.

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

1. Photosensitive composition

The photosensitive composition of the present invention comprises a polyester amide acid (A) obtained by reacting a tetracarboxylic acid dianhydride, a diamine and a polyhydric hydroxy compound as essential raw material components, a compound containing two or more polymerizable double bonds per molecule (E), an epoxy curing agent (F), and a molecular weight modifier (B) having a weight average molecular weight of 3,000 or less and containing 2 to 10 epoxy groups per molecule G). Wherein the total amount of the polymer (D) having an epoxy group and the epoxy compound (E) is 20 to 300 parts by weight, the 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) , And the content of the photopolymerization initiator (C) is more than 5.0 times the content of the molecular weight modifier (G) and less than 30 times. In addition, the photosensitive composition of the present invention may further contain other components than the above 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 is obtained by reacting tetracarboxylic dianhydride, diamine and polyhydric hydroxy compound as essential raw material components. More specifically, it is obtained by reacting X mol of tetracarboxylic dianhydride, Y mol of diamine and Z mol of polyhydric hydroxy compound at a ratio in which the relationship of the following formulas (1) and (2) is satisfied.

0.2? Z / Y? 8.0 (1)

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

The polyester amide acid has a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

In the formulas (3) and (4), R ¹ is a residue excluding two -CO-O-CO- from a tetracarboxylic acid dianhydride, and preferably an organic group having 2 to 30 carbon atoms. R ² is a residue other than -NH ₂ from a diamine, preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue excluding two -OH from the polyhydric hydroxy compound, preferably an organic group having 2 to 20 carbon atoms.

The synthesis of the polyester amide acid requires at least a solvent and may be a liquid or gel photosensitive composition in which the solvent is left as it is in consideration of handling properties and the solid composition may be prepared by removing the solvent . In the synthesis of the polyester amide acid, at least one compound selected from a monohydroxy compound and a styrene-maleic anhydride copolymer may be contained as a raw material if necessary, and among them, a monohydroxy compound . The synthesis of the polyester amide acid may also contain, as a raw material, other compounds than those described above, as needed, without impairing the object of the present invention. 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 a polyester amide acid. 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 a polyester amide acid. Specific examples of preferred diamines include 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, [4- (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

In the present invention, a polyhydric hydroxy compound is used as a material for obtaining a polyester amide acid. Specific examples of the preferable polyhydric hydroxy compound are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, Polypropylene glycol having an average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, Pentanediol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6-hexanetriol, 1,2-heptanediol, 1,7- Heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6-octanediol, 1,2,8-octanetriol, , 1,9-nonanediol, 1,2,9-nonanthiol, 1,2-decanediol, 1,10-decanediol, 1,2,10-decanediol, 1,12-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, diethanolamine, and triethanolamine. One or more of these may be used.

Among them, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Dihydroxydicyclohexyl, and isocyanuric acid tris (2-hydroxyethyl) are more preferable, and 1,4-butanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol are particularly preferred.

1-1-4. Monohydroxy compound

In the present invention, a monohydroxy compound may be used as a material for obtaining a polyester amide acid. By using the monohydroxy compound, the storage stability of the photosensitive composition is improved. Specific examples of preferred monohydroxy compounds include benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyloxetane and dimethylbenzylcarbinol. One or more of these may be used.

Among these, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane are more preferable. Considering the compatibility when a polyester amide acid produced by using these, a polymer having an epoxy group, an epoxy compound and an epoxy curing agent are mixed, and a coating property of the photosensitive composition on a color filter, the monohydroxy compound includes benzyl alcohol Is particularly preferable.

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 tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound. More preferably 5 to 200 parts by weight.

1-1-5. Styrene-maleic anhydride copolymer

The polyester amide acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the raw material. By doing so, the transparency 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, Kawahara Oil Company). 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

The synthesis of the polyester amide acid may include raw materials other than those described above as needed as far as the object of the present invention is not impaired, and examples of such other raw materials include silicon-containing monoamines .

Specific examples of preferred silicon-containing monoamines for use in the present invention are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane , 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyl Methyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. One or more of these 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 is preferably contained in an amount of 0 to 300 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound. More preferably 5 to 200 parts by weight.

1-1-7. Solvent used for synthesis reaction of polyester amide acid

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amide acid include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol mono Ethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, and cyclohexanone. Of these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether are preferable.

1-1-8. Synthesis method of polyester amide acid

In the method for synthesizing the polyester amide acid used in the present invention, X mole of a tetracarboxylic dianhydride, Y mole of a diamine, and Z mole of a polyhydric hydroxy compound are reacted in the solvent. At this time, 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 to be used in the present invention is a polyester amide acid in which a molecule having an acid anhydride group (-CO-O-CO-) at the end thereof has an amino group or a hydroxyl group at the end thereof under the condition that X is excessively used relative to Y + Is thought to be generated in excess of the molecule. 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 obtained by adding and reacting the monohydroxy compound is improved in compatibility with the epoxy compound and the epoxy curing agent, and the applicability of the photosensitive composition of the present invention containing them is improved.

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 of the present invention containing a polyester amide acid obtained by adding and reacting a silicon-containing monoamine is used, the acid resistance of the obtained cured film is improved. When the reaction is carried out by the above-described monomer composition, the monohydroxy compound and the silicon-containing monoamine may be added and reacted.

The reaction solvent is preferably used in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the tetracarboxylic acid 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 of previously reacting a carboxylic acid dianhydride and a polyhydric hydroxy compound and then adding a diamine to the reaction product or a method of reacting a tetracarboxylic dianhydride with a diamine in advance and then adding a polyhydric hydroxy compound And a method of adding an organic solvent to the solution.

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 is completed, the reaction solution is cooled to 40 ° C or lower, and then the silicon-containing monoamine is added, The reaction is carried out at 10 to 40 ° C for 0.1 to 6 hours. The monohydroxy compound may be added at any point in the reaction.

The polyester amide acid 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 bonded to the tetracarboxylic acid dianhydride, diamine or polyhydric hydroxy compound An amino group or a hydroxyl group, or an additive other than these compounds constitutes the terminal. By including such a constitution, the curability is improved.

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

The weight average molecular weight in this specification is a 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. On the other hand, the weight average molecular weights of commercially available products in this specification are the catalog 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 having a polymerizable double bond used in the present invention is not particularly limited, but a compound having two or more polymerizable double bonds per molecule is preferable. With respect to 100 parts by weight of the polyester amide acid, the compound having a polymerizable double bond is preferably 20 to 300 parts by weight since the residual film ratio after development becomes favorable.

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 (meth) Acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, , Epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di ) 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 modified with ethylene oxide, tri (meth) acrylate modified with ethylene oxide, epichlorohydrin modified (meth) acrylate modified with phosphoric acid, (Meth) acrylate, isobutylene di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neopentyl glycol modified trimethylol propane di Diacrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified tris [(meth) acryloxyethyl] isocyanurate, (meth) acrylated isocyanurate, phenylglycidyl ether acrylate hexamethylene Diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene di Cyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexamethylene diisocyanate Urethane prepolymer, non-yellowing type oligourethane acrylate, and carboxylic acid-containing urethane acrylate oligomer.

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, or 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 the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M-306 (65 to 70 wt%), M-305 (55 to 63 wt%), M-303 %), M-452 (25-40 wt%) and M-450 (less than 10 wt%, hereinafter abbreviated as M-450) (all trade names: Doa Synthetic Co., Ltd., pentaerythritol tri Acrylate content). 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 to 40 wt%), M-406 (25 to 35 wt%), and M-405 (10 to 20 wt% ; The content ratio in parentheses is 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 to 13% by weight, hereinafter abbreviated as "M-315" Trade name, manufactured by Toa Seisakusho Co., Ltd., content in parentheses is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture).

1-2-2. A compound having at least one polymerizable double bond per molecule and at least one functional group selected from -OH and -COOH

The photosensitive composition of the present invention may further contain a compound having one polymerizable double bond per molecule and at least one functional group selected from -OH and -COOH per molecule from the viewpoint of resolution. 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 used in an amount of 1 to 50 parts by weight per 100 parts by weight of the polyester amide acid, So that the property is preferable.

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-3-phenoxypropyl (Meth) acryloyloxyethyl methacrylate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, 4- (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono - (2-hydroxyphenyl), and? -Carboxyethyl (meth) acrylate.

Of these, 4-hydroxyphenyl (meth) acrylate and p-hydroxy (meth) acrylanilide are preferable because their resolution is improved.

1-3. The photopolymerization initiator (C)

The photopolymerization initiator contained in the photosensitive composition of the present invention is particularly limited as long as it can initiate polymerization of a composition containing a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, an epoxy curing agent and a molecular weight modifier It is not.

Examples of the photopolymerization initiator contained in the photosensitive composition of the present invention include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, Diethyl thioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclo Hexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, (IRGACURE 907, BASF Japan KK), 2- (dimethylamino) -1- (4-fluorophenyl) (Trade name: IRGACURE 369, BASF Japan Co., Ltd.), ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Isoamyl, 4,4'-di (t-butylperoxycarbo 2- (O-methyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- OXE04 (trade name, BASF Japan Co., Ltd.), 1,2-propanedione, 1- [4-ethylhexyloxypropane (ADEKA NCI-930, ADEKA Co., Ltd.), Adeka's NCI-831 (trade name; available from Dainippon Ink and Chemicals, Incorporated) (ADEKA), Adeka Optomer N-1919 (trade name, ADEKA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6 Bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6- 4'-dimethoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)] - 2,6- (Trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -Triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis -Diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4', 5,5'-tetraphenyl- , 2'-biimidazole, 2,2'-bis (2,4,6-trickle (2-methyl-2-dimethylaminopropionyl) carbazole, 3,6-bis (2 -methyl-2-morpholino-propionyl) -9-n- dodecyl carbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4- cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrolyl-1-yl) -phenyl) titanium.

The photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination. Of the photopolymerization initiators, α-aminoalkylphenone-based, acylphosphine oxide-based and oximeester-based photopolymerization initiators are preferable from the viewpoints of sensitivity of the coating film at the time of 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 heating to the drying are all referred to as " coating films ", and at any stage of the film formation process, for example, To indicate whether it is a coated film.

Among the photopolymerization initiators, 1- [4- [4- (2- (4-fluorophenyl) phenyl] Hydroxyethoxy) phenylthio] phenyl] -2- (O-acetyloxime) is preferably 20% by weight or more based on the total weight of the photopolymerization initiator from the viewpoints of sensitivity of the coating film and transparency of the cured film. 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 polymer (D) having an epoxy group

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

Polymers having epoxy groups are obtained by reacting glycidyl (meth) acrylate with other radically polymerizable monomers. Use of such a copolymer having an epoxy group is preferable because the transparency of the cured film obtained from the photosensitive composition is enhanced and the deterioration of transparency in the UV ozone treatment process and ultraviolet exposure process can be suppressed. Glycidyl (meth) acrylate preferably accounts for 50 to 99% by weight of all the monomers constituting the copolymer having an epoxy group from the viewpoints of flatness, heat resistance and solvent resistance.

Other radical polymerizable monomers include monofunctional (meth) acrylate, bifunctional (meth) acrylate and trifunctional or higher polyfunctional (meth) acrylate. In order to improve the heat resistance and chemical resistance of the cured film obtained from the photosensitive composition, it is preferable to use a trifunctional or more polyfunctional (meth) acrylate. On the other hand, the flatness of the cured film and the compatibility with the polyester amide acid , It is preferable to use monofunctional (meth) acrylate. However, since the heat resistance of the cured film, the smoothness of the solvent resistance and the flatness of the cured film, and the compatibility with the polyester amide acid in the composition tend to trade off, in order to exhibit these performances in a balanced manner, .

Preferable examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (Meth) acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate. These are preferable because compatibility with a polyester amide acid of a polymer having an epoxy group obtained by reacting with glycidyl (meth) acrylate is improved. The bifunctional (meth) acrylate is preferably contained in an amount of 1 to 30 parts by weight based on the total monomers to be used as a raw material for the polymer having an epoxy group from the viewpoints of flatness, heat resistance and chemical resistance.

The polymer having an epoxy group may contain a radical polymerizable monomer other than glycidyl (meth) acrylate and bifunctional (meth) acrylate as a raw material component. Such other radically polymerizable monomer is contained in an amount of 0 to 20% by weight from the viewpoint of exhibiting the properties of the other radically polymerizable monomer without impairing the effect of the present invention. As the other radical polymerizable monomer, the monofunctional (meth) acrylate and the trifunctional or more polyfunctional (meth) acrylate can be used.

Specific examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, m-phenoxybenzyl (meth) acrylate and tetrahydrofurfuryl .

Specific examples of the trifunctional or more polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate, trimethylolpropaneethoxy triacrylate, trimethylolpropane propoxy triacrylate, (2-acryloxyethyl) isocyanurate, glycerin ethoxy triacrylate, glycerin propoxy triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, Erythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.

The other radically polymerizable monomers may be used alone or in combination of two or more.

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

1-4-1. The solvent used for the synthesis reaction of the polymer having an epoxy group

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

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

These solvents may be used alone or in combination of two or more. If the proportion is 30% by weight or less based on the total amount of the solvent, a solvent other than the above solvent may be mixed and used.

1-4-2. Method for synthesizing a polymer having an epoxy group

A method of synthesizing a polymer having an epoxy group is not particularly limited, but radical polymerization in a solution using a solvent is preferable. When the reaction solvent is used in an amount of 100 parts by weight or more per 100 parts by weight of the total of the glycidyl (meth) acrylate, the bifunctional (meth) acrylate, and other radical polymerizable monomers used if necessary, It is preferable. The polymerization temperature is not particularly limited as long as a radical is sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 to 150 캜. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. Further, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

A known polymerization initiator may be used for the synthesis of the polymer having an epoxy group. Examples of the polymerization initiator include a compound capable of generating a radical by heat, an azo-based initiator such as azobisisobutyronitrile, and a peroxide-based initiator such as benzoyl peroxide. In the radical polymerization, an appropriate amount of a chain transfer agent such as thioglycolic acid may be added in order to control the molecular weight of the resulting copolymer.

The polymer having an epoxy group may be an epoxy compound solution in which the solvent used for synthesis is left as it is in consideration of handling property and the like. The solvent may be removed to obtain a solid epoxy compound taking into account the transportability and the like.

1-5. The epoxy compound (E)

The epoxy compound used in the present invention contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding an epoxy compound to the photosensitive composition of the present invention, the heat resistance of the cured film can be increased.

Preferable examples of the epoxy compound include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celloxide 2021P, (2-methyloxylanyl) -7-oxabicyclo [4.1.0] heptane (trade name, Celloxide 3000, Bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] ethyl] phenyl] -1-methylpropyl] phenyl] ethyl] phenoxy] -2-propanol in the form of a mixture of 1- [4- [1- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3- (Trade name: jER 1032H60, manufactured by Mitsubishi Chemical Corporation), 1,1,1-tris (4-hydroxyphenyl) Bis (oxiranyl (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.).

The total amount of the epoxy group-containing polymer (D) and the epoxy compound (E) is preferably from 20 to 200 parts by weight, based on 100 parts by weight of the polyester amide acid (A).

1-6. The epoxy curing agent (F)

In the photosensitive composition of the present invention, an epoxy curing agent is used to improve the flatness, chemical resistance and solvent resistance. Examples of the epoxy curing agent include acid anhydride type curing agents, amine type curing agents, phenol type curing agents, imidazole type curing agents, catalyst type curing agents, and thermosensitive acid generators such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts , An acid anhydride-based curing agent or an imidazole-based curing agent is preferable from the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film.

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 impairing the solubility of the photosensitive composition in a solvent are particularly preferable.

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

1-7. Molecular weight adjuster (G)

In the photosensitive composition of the present invention, a molecular weight regulator is used in order to suppress the increase in the molecular weight by polymerization and to exhibit excellent resolution. Molecular weight adjusting agents 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, 2-hydroxy-1,4-naphthoquinone, 1,2-benzoquinone, 1,4- Anthraquinone, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 1,4-dihydroxynaphthalene, 4-methoxyphenol, 2,2 ', 6,6'-tetra-t-butyl-4,4'-dihydroxybiphenyl, 3- (3,5- Butyl-4-hydroxyphenyl) propionic acid stearyl, 2,2'-methylenebis (6-t- Butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 4- hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, t-butyl-p-cresol, 4,4 (6-t-butyl-m-cresol), 4,4'-thiobis (6-t- Pentene, phenothiazine, and the like.

The molecular weight modifier may be used alone or in combination of two or more. Of the molecular weight regulators, naphthoquinone molecular weight regulators are preferred because they exhibit excellent resolution.

Among the molecular weight regulators, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferable from the viewpoint of resolution. It is more preferable that the content of the photopolymerization initiator is more than 5.0 times the content of the molecular weight regulator and the content of the photopolymerization initiator is more than 5.1 times the content of the molecular weight regulator, And more preferably 20 times or less. It is more preferable that the content of the photopolymerization initiator is more than 5.2 times the content of the molecular weight regulator, and the content of the photopolymerization initiator is 10 times or less.

1-8. A ratio of a polyester amide acid, a compound having a polymerizable double bond, a photopolymerization initiator, a polymer having an epoxy group, an epoxy compound, an epoxy curing agent,

In the photosensitive composition of the present invention, the ratio of the polymerizable double bond-containing compound to the polyester amide acid is from 20 to 300 parts by weight based on 100 parts by weight of the polyester amide acid. When the proportion of the compound having a polymerizable double bond is within this range, the balance of heat resistance, flatness, chemical resistance, and residual film ratio after development is satisfactory. More preferably, the compound having a polymerizable double bond is in a range of 100 to 300 parts by weight.

The ratio of the photopolymerization initiator to 100 parts by weight of the polyester amide acid is 2 to 60 parts by weight. The ratio of the photopolymerization initiator within this range is preferable from the viewpoint of the sensitivity of the coating film upon exposure.

In the photosensitive composition of the present invention, the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound to 100 parts by weight of the polyester amide acid is 20 to 200 parts by weight. When the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is in this range, the balance between heat resistance and flatness is good. More preferably, the total amount of the epoxy compound-containing polymer and the epoxy compound is in the range of 20 to 150 parts by weight.

The ratio of the epoxy curing agent to the total amount of the polymer having an epoxy group and the epoxy compound is 0.1 to 60 parts by weight of the epoxy curing agent with respect to 100 parts by weight of the total amount of the polymer having an epoxy group and the epoxy compound. For example, it is preferable to add the epoxy curing agent so that the amount of the carboxylic anhydride group or the carboxyl group in the epoxy curing agent is 0.1 to 1.5 times as much as the amount of the epoxy curing agent in the case of the acid anhydride curing agent. At this time, the carboxylic acid anhydride group is calculated two times. More preferably 0.15 to 0.8 parts by weight of the carboxylic acid anhydride group or the carboxyl group because the chemical resistance is further improved.

1-9. Other components

Various additives may be added to the photosensitive composition of the present invention in order to improve coating uniformity and adhesiveness. The additives include antioxidants such as solvents, photoacid generators, anionic, cationic, nonionic, fluorine or silicon surfactants, adhesion improvers, hindered phenols, hindered amines, phosphorus, .

1-9-1. solvent

A solvent may be added to the photosensitive composition of the present invention. The solvent optionally added to the photosensitive composition of the present invention is preferably a solvent in which a polyester amide acid, a compound having a polymerizable double bond, an epoxy compound, an epoxy curing agent and the like are dissolved. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethyl ethoxyacetate, Methyl propionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, Methyl propionate, methyl 2-methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Methyl propionate, methyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid, , Ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol mono Ethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. The solvent may be one of these, or a mixture of two or more thereof.

1-9-2. Photoacid generator

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

Specific examples of the 1,2-quinonediazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzo Phenone-1,2-naphthoquinonediazide-5-sulfonic acid ester (for example, trade name: NT-200 available from Toyo Synthetic Chemical Industry Co., Ltd.), 2,4,6-trihydroxybenzophenone- Toquinonediazide-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 (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 4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '- [1- [4- [ Methylphenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4 '- [1- [4- [1- [4- Phenyl] -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- 7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'- tetramethyl-1,1'-spirobindene -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-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.

1-9-3. Surfactants

A surfactant may be added to the photosensitive composition of the present invention 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, Disperbyk-161, BYK-310, BYK-310, BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 Ltd.), Surflon S611 (trade name, available from AGC Seiyam Chemical Co., Ltd.), KP-341, KP-368, KF-96-50CS, KF- (All trade names, Neos), Megapox F-410 (trade name, manufactured by Nissan Chemical Industries, Ltd.), Fujitsu F-410, Fujitsu F- Megapack F-554, Megapack F-554, Megaplock F-474, Megapack F-552, Megapack F-553, Megapack F-554, Megapak F- Parkfax F-555, Megafock F-556, Megafock F-558, Megafox 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, and TEGO Rad 2200N (all trade names, Ebonic Degussa Japan KK), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether , Fluoroalkylammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonic acid salt, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene Nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene But are not limited to, ethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan palaurate, sorbitan stearate, sorbitan oleate, Sorbitan monostearate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate and Alkyl diphenyl ether disulfonate 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, F-477, Megafac F-556, Megafac F-559, Megapack RS-72-K, Megapak DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoro At least one selected from alkyl polyoxyethylene ether, fluoroalkylsulfonic acid salt, fluoroalkyltrimethylammonium salt, and fluoroalkylaminosulfonic acid salt is preferable because uniformity of application 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 wt% with respect to the total amount of the photosensitive composition.

1-9-4. Adhesion improving agent

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

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples 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.

1-9-5. Macromonomers having a polymerizable double bond

The photosensitive composition of the present invention may further contain a macromonomer having a polymerizable double bond from the viewpoint of adhesion described in the preceding paragraph.

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

Examples of such macromonomers available as commercial products include mono-terminated methacryloylated polymethyl methacrylate oligomers (Mn = 6,000, trade name: AA-6, manufactured by Doja Kasei Co., Ltd.) and mono-terminated methacryloyl- (Mn = 6,000, trade name: AS-6, manufactured by Doa Kagaku Kogyo Co., Ltd.) was used as a polymerization initiator (Mn = 6,000, trade name: AB- ).

1-9-6. Antioxidant

The photosensitive composition of the present invention may further contain an antioxidant from the viewpoints of improving transparency and preventing yellowing when the cured film is exposed to high temperatures.

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

1-10. 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.

2. The cured film obtained from the photosensitive composition

The photosensitive composition of the present invention can be produced by mixing a polyester amide acid, a compound having a polymerizable double bond, a polymer having an epoxy group, an epoxy compound, an epoxy curing agent and a molecular weight modifier, , Surfactants, and other additives, if necessary, and mixing them uniformly and dissolving them.

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 70 to 150 DEG C for 5 to 15 minutes in an oven and 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 a compound 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 coating film, the cured film can be obtained by heating at 180 to 250 캜, preferably 200 to 250 캜, for an oven for 30 to 90 minutes and for a hot plate for 5 to 30 minutes.

When the cured film thus obtained is heated, furthermore, 1) the polyamic acid portion of the polyester amide acid is dehydrated and cyclized to form an imide bond, and 2) the carboxylic acid of the polyester amide acid is a polymer having an epoxy group And is thus very strong, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputter resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state image 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 when used as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the orientation film. Further, the cured film of the present invention is also effective as a protective film for an LED light-emitting body.

Example

EXAMPLES Next, the present invention will be described concretely with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited at all by these Examples. The abbreviations of various materials in Tables 1 and 2 will be described below. M-402 is a polymerizable double bond-containing compound ARONIX M-402 (trade name, manufactured by Toa Gosei Co., Ltd.), NCI-930 is a photopolymerization initiator ADEKA COULSE NCI-930 (trade name: ADEKA), VG3101L is an epoxy compound TECHMORE VG3101L (Trade name, manufactured by JNC Corporation), MP200 is a coupling agent COATOSIL MP200 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), EHPE3150 is an epoxy compound EHPE3150 F-556 is a surfactant Megapak F-556 (trade name, manufactured by DIC Co., Ltd.), MMP is a surfactant commercially available from Mitsubishi Kasei Kogyo Co., Ltd., and AO-60 is an antioxidant ADK STAB AO- Solvent 3-methoxypropionate methyl, PGMEA is solvent propylene glycol monomethyl ether acetate, and EDM is solvent diethylene glycol ethyl methyl ether.

In addition, VG3101L can be prepared by reacting 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3- Propane (molecular weight = 593) 90% by weight and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [4- (Molecular weight = 1,129), and EHPE 3150 is a compound represented by the molecular formula C ₁₂₆ H ₁₉₄ O ₃₃ , And a molecular weight of 2,237 (all refer to the product safety data sheet).

First, a solution of a polyester amide acid (A) comprising a reaction product of a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound and the like, and a solution of the polymer (D) having an epoxy group was synthesized as shown below Synthesis Examples 1 and 2).

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

 In a four-necked flask equipped with a stirrer, PGMEA, BT-100, SMA1000P dehydrated and purified (trade name: styrene · maleic anhydride copolymer, Kawahara Oil Co., Ltd.), 1,4-butanediol, And the mixture was stirred at 125 DEG C for 3 hours under a nitrogen stream.

PGMEA 481.37 g

BT-100 34.47 g

SMA1000P 164.11g

10.45 g of 1,4-butanediol

Benzyl alcohol 50.17 g

Thereafter, the reaction solution was cooled to 25 DEG C, 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as DDS) and PGMEA were added in the following weights, and the mixture was stirred at 20 to 30 DEG C for 2 hours, Followed by stirring at 125 DEG C for 2 hours.

DDS 10.80g

PGMEA 148.63 g

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

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

[Synthesis Example 2] Synthesis of polymer (D) solution having epoxy group

MMP obtained by dehydration and purification as a polymerization solvent in a four-necked flask equipped with a stirrer, glycidyl methacrylate as a radically polymerizable compound (a1) having an epoxy group and diethylene glycol dimethacrylate (NK) as another polymerizable compound (a2) (2-methylpropionate) (V-601, trade name; manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator Ltd.) was weighed in the following weight and stirred at 110 DEG C for 2 hours in a dry nitrogen stream.

MMP 31.50g

12.15 g of glycidyl methacrylate

1.35 g of diethylene glycol dimethacrylate

V-601 2.03 g

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

[Example 1]

A 1000 ml separable flask equipped with a stirring wing was purged with nitrogen and 40.00 g of the polyester amide acid (A) solution obtained in Synthesis Example 1 and 60.00 g of M-402 as a compound having a polymerizable double bond , 1.2 g of NCI-930 as a photopolymerization initiator, 12.00 g of a polymer (D) solution having an epoxy group, 1.2 g of EHPE3150 as an epoxy compound, 2.0 g of trimellitic anhydride (hereinafter abbreviated as "TMA") as an epoxy curing agent, and 3 g of glycidyloxypropyltrimethoxysilane polymer (trade name: COATOSIL MP 200, Momentive Performance Material Co., Ltd. ), 0.64 g of NT-200 (trade name, manufactured by Toyo Synthetic Chemical Industry Co., Ltd.), 0.06 g of ADK STAB AO-60 (trade name: ADEKA), 4.1 g of dehydrated and purified MMP as a solvent, and 22.0 g of PGMEA g, and the mixture was stirred at room temperature for 3 hours to dissolve uniformly. Subsequently, 0.02 g of Megafac F-556 (trade name: DIC Co., Ltd.) was added, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 탆) to prepare a photosensitive composition.

[Examples 2 to 4]

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

[Comparative Examples 1 to 4]

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

Each of the photosensitive compositions obtained above was spin-coated on a glass substrate at 550 rpm for 10 seconds and prebaked on a hot plate at 100 캜 for 80 seconds. Subsequently, the resist film was exposed in the air using a proximity photoresist TME-150PRC (trade name: Topcon Co., Ltd.). The exposure amount was 30 mJ / cm 2, as measured with a cumulative photometer UIT-102 (trade name, manufactured by Ushio Co., Ltd.) and a photodetector UVD-365 PD (trade name, manufactured by Ushio Co., Ltd.). The coated film after exposure was developed for 40 seconds using a buffer solution of sodium carbonate / sodium hydrogencarbonate at 27 DEG C, and then the coating film was washed with pure water for 20 seconds and then dried with a hot plate at 100 DEG C for 2 minutes. Post baking was performed at 230 캜 for 30 minutes to obtain a glass substrate 1 having a cured film having a film thickness of 3.0 탆.

A glass substrate (2) with a cured film was obtained from each photosensitive composition in accordance with the above-described method for producing the glass substrate (1) with a cured film, except that the glass substrate was changed to an ITO-attached glass substrate.

The glass substrate 1 with a cured film was used to measure the residual film ratio, adhesion, chemical resistance, heat resistance and transparency of the film after the development by using the glass substrate 2 with a cured film to determine adhesion and chemical resistance I appreciated.

[Evaluation method of residual film ratio after development]

The film thickness before development and the film thickness after development of the glass substrate 1 with a cured film were measured using a step, surface roughness and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.) The residual film ratio after development was calculated. The case where the residual film ratio after development 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 &

Film thickness after development = (film thickness after development / film thickness before development) x 100

[Production of substrate for evaluation of resolution]

Next, the photosensitive composition was spin-coated on a glass substrate at 550 rpm for 10 seconds and prebaked on a hot plate at 100 캜 for 80 seconds. Then, exposure was carried out with an exposure gap of 100 占 퐉 using a proximity phototray TME-150 PRC via a mask having holes and line patterns of 30 占 퐉 width in the air. The amount of exposure was measured to 30 mJ / cm 2 by measuring with an integrated photometer UIT-102 and a photoconductor UVD-365PD. The coated film after exposure was developed for 40 seconds using a buffer solution of sodium carbonate / sodium hydrogencarbonate at 27 DEG C, and then the coating film was washed with pure water for 20 seconds and then dried with a hot plate at 100 DEG C for 2 minutes. Post baking was performed at 230 캜 for 30 minutes in an oven to obtain a glass substrate 3 on which a cured film having a film thickness of 3.0 탆 was formed.

The cured film thus obtained was evaluated for its resolution.

[Evaluation method of resolution]

The obtained patterned glass substrate 3 with a cured film was observed with a 1,000-fold optical microscope, and the resolution of holes and line patterns corresponding to a mask size of 30 mu m in width was evaluated. 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 heat resistance]

The glass substrate 1 with the cured film thus obtained was reheated at 230 DEG C for 1 hour, and then the film thickness before heating and the film thickness after heating were measured, and the film residual ratio after heating was calculated by the following equation to evaluate the heat resistance . For the measurement of the film thickness, P-16 was used. A case where the residual film ratio after heating was 95% or more was evaluated as & cir & and a case where the residual film ratio after heating was less than 95% was evaluated as x.

Film thickness after heating = (film thickness after heating / film thickness before heating) x 100

[Evaluation method of transparency]

The transmittance of the cured film only at a wavelength of 400 nm was measured by the ultraviolet visible near infrared spectrophotometer (trade name: V-670, Nihon Spectroscopy Co., Ltd.) in the glass substrate 1 with the cured film obtained above, I appreciated. A case where the transmittance was 95% or more was evaluated as & cir & and a case where the transmittance was less than 95% was evaluated as &

[Evaluation method of adhesion]

The adhesion was evaluated in accordance with JIS K 5600-5-6 (crosscut test). That is, cuts were made so as to form 100 squares of 1 mm x 1 mm square on the glass substrates 1 and 2 with cured films obtained above, and a cellophane tape (3M, Scotch (TM) Tape No. 610) was attached to the tape, and then peeled off. The case where the cured film in the scale is not peeled off at all, the case where less than one-third of the cured film in the scale is peeled is?, And the case where more than one-third is peeled is x.

[Evaluation method of chemical resistance]

The glass substrates 1 and 2 with the cured films thus obtained were immersed in an ITO etchant (trade name: ITO-301, manufactured by Kanto Kagaku Co., Ltd.) at 25 ° C for 6 minutes and then rinsed with pure water to wipe out the water. Further, cuts were made so as to form 100 squares with a square of 1 mm x 1 mm, a tape peeling test was carried out in which a cellophane tape (3M, Scotch (TM) cellophane tape No. 610) , And chemical resistance. The case where the cured film in the scale is not peeled off at all, the case where less than one-third of the cured film in the scale is peeled is?, And the case where more than one-third is peeled is x.

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

 As is clear from the results shown in Table 3, the cured films of Examples 1 to 4 are excellent in residual film ratio after development, resolution, heat resistance, transparency, adhesion, and chemical resistance. On the other hand, the cured films of Comparative Examples 1 to 4 do not become "? &Quot; As described above, when a polyester amide acid obtained by reacting tetracarboxylic acid dianhydride, diamine and polyhydric hydroxy compound as essential raw material components is used, when the molecular weight of the epoxy compound is within the range of the present invention, .

Since the cured film obtained from the photosensitive composition of the present invention is excellent in optical characteristics such as transparency, heat resistance, flatness, resolution and chemical resistance, it is preferable to use a protective film for various optical materials such as color filters, LED light emitting devices and light receiving devices, , A transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

Claims (16)

(A), a polymerizable double bond-containing compound (B), a photopolymerization initiator (C), an epoxy group-containing polymer (D), an epoxy compound (E), an epoxy curing agent (F) As a photosensitive composition;
The polyester amide acid (A) is obtained by reacting X mole of a tetracarboxylic acid dianhydride, Y mole of a diamine and Z mole of a 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 polymer (D) having an epoxy group has a weight average molecular weight of 3,000 to 50,000;
The epoxy compound (E) contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000;
The total amount of the 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 polymer (D) having the epoxy group and the epoxy compound (E) Is 20 to 200 parts by weight;
Wherein the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier (G).
0.2? Z / Y? 8.0 (1)
0.2? (Y + Z) /X? 5.0 (2)

In 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 further comprises a monohydroxy compound. 3. The method of claim 2,
Wherein the monohydroxy compound is at least one selected from isopropyl alcohol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane. 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 Or more;
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, isocyanuric acid ethyleneoxide- Modified (meth) acryl oligomer in an amount of 50% by weight or more based on the total weight of the compound having a polymerizable double bond;
The photopolymerization initiator (C) is at least one selected from an? -Aminoalkylphenone-based, acylphosphine oxide-based, oximeester-based photopolymerization initiator;
Wherein the polymer (D) having an epoxy group has an epoxy group as a reaction product from a mixture of a radically polymerizable monomer (d1) having an epoxy group and a radically polymerizable monomer (d2) other than the above (d1); And,
Wherein the epoxy curing agent (F) is at least one selected from trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. 5. The method of claim 4,
The radically polymerizable monomer (d1) having an epoxy group is prepared from glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether At least one selected;
wherein the radically polymerizable monomer (d2) other than (d1) comprises at least one bifunctional (meth) acrylate. 6. The method according to any one of claims 1 to 5,
Wherein the molecular weight modifier (G) is at least one selected from mercaptans, xanthogens, quinones, hydroquinones, and 2,4-diphenyl-4-methyl-1-heptene. 6. The method of claim 5,
Wherein 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 monohydroxy compound is benzyl alcohol;
The compound (B) having a polymerizable double bond is at least one selected from dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and polybasic acid modified (meth) acrylic oligomer;
Wherein the bifunctional (meth) acrylate is selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) (Meth) acrylate, neopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate;
Wherein the photopolymerization initiator (C) is at least one selected from the group consisting of 1,2-octanedione, 1- [4- (phenylthio) phenyl] -, 2- (O-benzoyloxime), ethanone, 1- [ -Methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime), and 1,2-propanedione, 1- [4- [4- (2-hydroxyethoxy) ] Phenyl] -2- (O-acetyloxime) in an amount of 50% by weight or more based on the total weight of the photopolymerization initiator (C);
Wherein the epoxy curing agent (F) is at least one selected from trimellitic anhydride and 2-undecylimidazole; And,
Further comprising at least one solvent selected from methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent. 8. The method according to any one of claims 1 to 7,
Wherein the molecular weight modifier (G) is at least one selected from naphthoquinones and hydroquinones. A cured film obtained from the photosensitive composition according to any one of claims 1 to 8. A color filter having the cured film of claim 9 as a transparent protective film. A display element using the color filter of claim 10. A solid-state imaging device using the color filter of claim 10. A display element using the cured film of claim 9 as a transparent insulating film formed between a TFT and a transparent electrode. A display element using the cured film of claim 9 as a transparent insulating film formed between a TFT and an orientation film. An LED light source using the cured film of claim 9 as a protective film. An interlayer insulating film having the cured film of claim 9 as a transparent protective film.