KR20180023781A - Polyester amide acids and photosensitive compositions containing the same - Google Patents

Abstract

The present invention relates to a polyester amide acid (A) which is a constituent component of a photosensitive composition having excellent resolution and a residual film ratio. The polyester amide acid (A) comprises X-mole of tetracarboxylic dianhydride, Y-mole of diamine, Z-mole of polyhydric hydroxy compound, and W-mole of cationic polymerizable cyclic ether compound having a polymerizable double bond at a ratio that satisfies the relation of formula (1), 0.2<=Z/Y<=8.0, formula (2), 0.2<=(Y+Z)/X<=5.0, and formula (3), 0.05<=W/2X<=1.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyester amide acid and a photosensitive composition containing the polyester amide acid and a photosensitive composition containing the polyester amide acid.

The present invention relates to a photosensitive polymer and a photosensitive composition comprising the photosensitive polymer. A cured film formed of the photosensitive composition, a color filter using the cured film, an insulating film, a protective film, and the like. The present invention also relates to a process for producing the photosensitive polymer.

In a device such as a display element, a chemical treatment or a high-temperature heat treatment is performed on a surface thereof in a conventional manufacturing process. A protective film is formed on the surface of the device in order to prevent deterioration, damage and alteration due to the treatment. The protective film is required to have satisfactory resolution and residual film ratio in addition to heat resistance, chemical resistance, adhesion to a substrate, transparency, flatness and the like.

In order to form a protective film, a thermosetting composition or a photosensitive composition is widely used. In the case of the thermosetting composition, the volatile matter generated during the film formation is suppressed to a small extent, and the heat resistance is excellent. However, in the case of using a thermosetting composition, it is difficult to form a scribe line, and a process of cleaning debris generated at the time of panel division is required.

On the other hand, when the photosensitive composition is used, the scribe line is easily formed, and the moldability is excellent. For this reason, the need for forming a protective film increases in a photosensitive composition capable of fine molding (fine patterning).

However, in order to form an excellent fine pattern shape, it is required that the photosensitive composition has an appropriate balance between resolution and residual film ratio while maintaining proper solubility in a developing solution. If the solubility of the unexposed portion is increased in order to improve the resolution, the solubility of the exposed portion increases and the residual film ratio decreases. On the other hand, if the solubility of the exposed portion is lowered in order to increase the residual film ratio, the solubility of the unexposed portion is also lowered and the resolution is lowered. That is, it is necessary to select an appropriate composition ratio so that the solubility of the exposed portion is high and the solubility of the unexposed portion is low. However, the kind of the members constituting the conventional photosensitive composition such as an alkali soluble resin, a photo polymerization initiator, a solvent, It was difficult to balance the resolution and retention rate only by adjusting the composition ratio. Therefore, recently, studies for obtaining a balance between resolution and residual film ratio by introducing a photosensitive group into a polymer as a base of a composition have been actively conducted.

For example, as shown in Patent Document 1, Patent Document 2, and Patent Document 3, development of a photosensitive polymer which introduces a polymerizable double bond to a polyimide precursor to impart an appropriate balance of resolution and residual film ratio has been attempted . However, as for the photosensitive composition containing these photosensitive polymers, there is no substrate of a marine size that can be practiced in the literature, and the production process of the photosensitive polymer is complicated, and the available raw materials are limited according to the production conditions. have.

Japanese Patent Application Laid-Open No. 2005-154643 Japanese Patent Application Laid-Open No. 2006-291221 Japanese Patent Application Laid-Open No. 2006-193691

The object of the present invention is to provide a polyester amide acid which is a constituent component of a photosensitive composition having excellent resolution and residual film ratio.

The present inventors have intensively studied in order to solve the above-mentioned problems. As a result, they have found that a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond The present inventors have found that the photosensitive composition containing an ester amide acid has excellent balance of resolution and residual film ratio while maintaining proper solubility in a developing solution. The present invention includes the following configuration.

[1] A reaction product of a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond,

(1), wherein X is a tetra carboxylic acid dianhydride, Y is a diamine, Z is a polyhydric hydroxy compound, and W is a polymerizable double bond. , The formula (2) and the formula (3) are satisfied.

0.2? Z / Y? 8.0 (1)

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

0.05? W / 2? X? 1.0 (3)

[2] A reaction product of the raw material further comprising a compound having three or more acid anhydride groups,

Among the raw materials, a tetondricarboxylic acid dianhydride of X mole, a diamine of Y mole, a polyhydric hydroxy compound of Z mole, a cationically polymerizable cyclic ether compound having a polymerizable double bond of W mole, and an acid anhydride group of V mole The polyester amide acid (A) according to the item [1], wherein the polyester amide acid (A) according to item [1] contains a compound having three or more compounds in the ratio satisfying the relations of the following formulas (1), (2) and

0.2? Z / Y? 8.0 (1)

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

0.0 &gt; W / (2X + rV) &lt; / RTI &gt;

The compound having three or more acid anhydride groups includes r acid anhydride groups per molecule and is used in an amount of 0.1 to 500 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride, diamine, and polyhydric hydroxy compound.

[3] The polyester amide acid (A) according to [1] or [2], which comprises a constituent unit represented by the following formula (4) and a constituent unit represented by the formula (5)

Wherein R &lt; ¹ &gt; is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R &lt; ^{2 &} The removal of the two -NH ₂ from the diamine residue, R ³ is hydroxy and the polyvalent residue obtained by removing two hydroxy compound from -OH, R ⁵ is H or independently a group having the polymerizable double bond, and

R ⁵ in the polyester amide acid (A) is not all H.

[4] The polyester amide acid (A) according to [1] or [2], further comprising a monohydroxy compound in the raw material.

[5] The polyester amide acid (A) according to [4], which comprises a constituent unit represented by the following formula (4), a constituent unit represented by the formula (5) and a constituent unit represented by the formula (6)

Wherein R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, and R ³ is a residue obtained by removing a polyhydric hydroxy compound R ⁴ is a residue obtained by removing -OH from the monohydroxy compound, R ⁵ is independently a group having H or a polymerizable double bond, and

R ⁵ in the polyester amide acid (A) is not all H.

[6] The cationically polymerizable cyclic ether compound having a polymerizable double bond has a (meth) acryloxy group,

The polyester amide acid (A) according to [1], [2] or [4], having a glycidyl group or an oxetanyl group.

[7] The cationically polymerizable cyclic ether compound having a polymerizable double bond is selected from glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, Epoxy heptyl acrylate, 6,7-epoxy heptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl Benzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate,

3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) Acrylic acid esters such as 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane and 3- 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3-ethyloxetane. At least one polyester amide acid (A) according to [1], [2] or [4].

[8] The tetracarboxylic acid dianhydride may be at least one selected from the group consisting of 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylether tetracarboxylic acid dianhydride , 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and ethylene glycol bis (anhydrotrimellitate ) And at least one compound selected from the group consisting of

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

The polyhydric hydroxy compound may be at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, isocyanurate tris (2-hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, The polyester amide acid (A) according to [1], [2] or [4], which is at least one selected from the group consisting of 2- (4-hydroxyphenyl) ethanol.

[9] The polyester amide acid (A) according to [2] or [4], wherein the compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer.

[10] The method according to [4], wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether and 3-ethyl-3-hydroxymethyloxetane. Polyester amide acid (A).

[11] A resin composition comprising the polyester amide acid (A), the compound (B) having a polymerizable double bond, the photopolymerization initiator (C), the epoxy compound (D) (E).

[12] The photosensitive composition according to [11], wherein the polyester amide acid (A) has a weight average molecular weight of 1,000 to 200,000.

The polyester amide acid related to the embodiment of the present invention can constitute a photosensitive composition having excellent heat resistance, transparency and flatness as well as resolution and residual film ratio by introducing a polymerizable double bond. The cured film formed by the photosensitive composition can be applied to various applications such as a color filter, a protective film, and an insulating film.

1. Polyester amide acid (A)

The polyester amide acid (A) related to embodiments of the present invention is a reactant of a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond . The raw material is obtained by reacting X-mole of tetracarboxylic dianhydride, Y-mole of diamine, Z-mole of polyhydric hydroxy compound, and W-mole of polymerizable double bond of a cationically polymerizable cyclic ether compound, 1), (2) and (3).

0.2? Z / Y? 8.0 (1)

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

0.05? W / 2? X? 1.0 (3)

Further, in the present specification, for the purpose of clarifying the structural features of the polyester amide acid (A) in comparison with other materials used in combination with the polyester amide acid (A), the term "polyester amide acid May be indicated.

The polyester amide acid (A) may be a reactant of the above-mentioned raw materials further comprising a compound having three or more acid anhydride groups. In this case, in the raw material, a mixture of X mole of tetracarboxylic dianhydride, Y mole of diamine, Z mole of polyhydric hydroxy compound, W mole of polymerizable double bond and cationic polymerizable cyclic ether compound, and V mole of acid A compound having three or more anhydride groups is contained in a ratio in which the relationship of the following formulas (1), (2) and (3 ') is satisfied.

0.2? Z / Y? 8.0 (1)

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

0.0 &gt; W / (2X + rV) &lt; / RTI &gt;

The compound having three or more acid anhydride groups includes r acid anhydride groups per molecule and 0.1 to 300 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydric hydroxy compound.

The polyester amide acid (A) has a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5).

Wherein R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, and R ³ is a residue obtained by removing a polyhydric hydroxy compound And R &lt; ⁵ &gt; are independently H or a group having a polymerizable double bond. In addition, the R ⁵ in the polyester amide acid (A) is not all H.

The polyester amide acid (A) according to another embodiment of the present invention is a reactant of the raw materials further comprising a monohydroxy compound. In this case, the raw material may or may not contain a compound having three or more of the above-mentioned acid anhydride groups. The polyester amide acid (A) in this case has a structural unit represented by the following formula (4), a structural unit represented by the formula (5) and a structural unit represented by the formula (6).

Wherein R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, and R ³ is a residue obtained by removing a polyhydric hydroxy compound R ⁴ is a residue obtained by removing -OH from the monohydroxy compound, and R ⁵ is independently a group having H or a polymerizable double bond. In addition, the R ⁵ in the polyester amide acid (A) is not all H.

The synthesis of the polyester amide acid (A) related to the embodiment of the present invention requires at least a solvent. The solvent may be left as it is to be a liquid or gel-like photosensitive composition in consideration of handling property and the like. Alternatively, the solvent may be removed to form a solid photosensitive composition in consideration of transportability and the like.

In addition, the synthesis of the polyester amide acid (A) may include other compounds other than the above insofar as the object of the present invention is not impaired.

1-1. Tetracarboxylic dianhydride

In the present invention, a tetracarboxylic acid dianhydride is used as a material for obtaining the polyester amide acid (A). Specific examples of the tetracarboxylic acid dianhydride include 4,4'-diphenylether tetracarboxylic dianhydride (hereinafter, sometimes abbreviated as ODPA), 1,2,3,4- Butane tetracarboxylic acid dianhydride (hereinafter abbreviated as BT-100 in some cases).

Examples of the tetracarboxylic acid dianhydride which can be used in the present invention include, in addition to the above-mentioned compounds, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenonetetra Carboxylic acid dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ' 3,3'-diphenylsulfone 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 acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [ Bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitate) (TMEG-100, Shin-Nippon Rikagaku), cyclobutane tetracarboxylic acid Dianhydride, methylcyclobutane tetracarboxylic acid imine There may be mentioned, for example, water, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, ethanetetracarboxylic acid dianhydride, and butanetetracarboxylic dianhydride, and among the above tetracarboxylic dianhydrides At least one species may be used.

Among them, the tetracarboxylic acid dianhydride which gives good transparency to the cured film can be obtained by reacting 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl Ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, and TMEG- 100, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride and 1,2,3,4 -Butane tetracarboxylic acid dianhydride is preferred.

1-2. Diamine

In the present invention, a diamine is used as a material for obtaining the polyester amide acid (A). Specific examples of the diamine include 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as DDS) used in the examples.

Specific examples of the diamine that can be used in the present invention include, in addition to the above-mentioned compounds, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, and 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, and at least one of the above diamines can be used.

Of these, 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone are preferable from the viewpoint of imparting good transparency to the cured film, and 3,3'- Phenyl sulfone is more preferable.

1-3. Polyhydric hydroxy compound

In the present invention, a polyhydric hydroxy compound is used as a material for obtaining the polyester amide acid (A). Specific examples of the polyhydric hydroxy compound include 1,4-butanediol used in the examples.

Examples of polyhydric hydroxy compounds usable in the present invention include, in addition to the above-mentioned compounds, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, , Tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-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, trimethylolpropane, pentaerythritol Bisphenol S (bis (4-hydroxyphenyl) sulfone), dipentaerythritol, isocyanuric acid tris (2-hydroxyethyl) , Bisphenol F (bis (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, -Hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, and triethanolamine, and at least one of the polyhydric hydroxy compounds described above can be used.

Of these, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- heptanediol, 1,8- octanediol, isocyanuric acid tris 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- ((4-hydroxyphenyl) propyl) 4-hydroxyphenyl) ethanol is preferable because of its good solubility in a reaction solvent.

1-4. A cationically polymerizable cyclic ether compound having a polymerizable double bond

In the present invention, a cationically polymerizable cyclic ether compound having a polymerizable double bond is used as a material for obtaining the polyester amide acid (A). The cationically polymerizable cyclic ether compound having a polymerizable double bond is a compound having a (meth) acryloxy group and also having a glycidyl group or an oxetanyl group. Specific examples of the cationically polymerizable cyclic ether compound having a polymerizable double bond are preferably glycidyl methacrylate (hereinafter abbreviated as GMA in some cases), 4-hydroxybutyl acrylate Glycidyl ether (hereinafter may be abbreviated as 4HBAGE in some cases).

Specific examples of the cationically polymerizable cyclic ether compound having a polymerizable double bond that can be used in the present invention include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3 , 4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m- Glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate,

3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) Acrylic acid esters such as 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane and 3- 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3-ethyloxetane, and these May be used.

1-5. Compounds having three or more acid anhydride groups

In the present invention, as a material for obtaining the polyester amide acid (A), a compound having three or more acid anhydride groups may be used. This is preferable because transparency of the cured film is improved. The compound having three or more acid anhydride groups includes r acid anhydride groups per one molecule, and r is 3 to 50, preferably 3 to 25, more preferably 5 to 10.

Examples of the compound having three or more acid anhydride groups include styrene-maleic anhydride copolymer. The ratio (molar ratio) of each component constituting the styrene-maleic anhydride copolymer is styrene / maleic anhydride = 0.5 to 4, preferably 1 to 3. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

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

The styrene-maleic anhydride copolymer is preferably contained in an amount of 0.1 to 500 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride, the diamine, and the polyhydric hydroxy compound. More preferably 10 to 300 parts by weight.

1-6. Monohydroxy compound

In the present invention, a monohydroxy compound may be used as a material for obtaining the polyester amide acid (A). When the monohydroxy compound is used, the storage stability of the photosensitive composition is improved.

Specific examples of the monohydroxy compound include benzyl alcohol used in the examples.

Examples of the monohydroxy compound which can be used in the present invention include isopropyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether Ether, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethylbenzylcarbinol.

Among them, the use of benzyl alcohol is particularly preferable for the monohydroxy compound in consideration of the applicability to a color filter in the case of using a photosensitive composition.

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

1-7. Monoamine with alkoxysilyl

In the synthesis of the polyester amide acid (A) of the present invention, raw materials other than the above may be included as necessary in the range not hindering the object of the present invention. Examples of other raw materials include monosaccharides having alkoxysilyl Amines.

Specific examples of the alkoxysilyl monoamine used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyl 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenyltrimethoxysilane, -Aminophenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of them may be used.

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

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

The alkoxysilyl-containing monoamine can be added in order to react with the acid anhydride group at the terminal of the molecule and introduce the silyl group at the terminal, under the condition that X is excessively used for Y + Z within the range of the formula (2). The use of a photosensitive composition containing a polyester amide acid (A) obtained by adding a monoamine having an alkoxysilyl improves the acid resistance of the cured film.

1-8. Basic catalyst

In the synthesis of the polyester amide acid (A), other raw materials other than those described above may be contained as a raw material insofar as the object of the present invention is not impaired, and examples of other raw materials include basic catalysts.

Specific examples of the basic catalyst used in the present invention are preferably 1-methylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzoimidazole, 1,8-diazabicyclo And nitrogen-containing heterocyclic compounds such as [5.4.0] -7-undecene, and tertiary amines such as 2- (dimethylaminomethyl) phenol, triethylamine and dimethylbenzylamine. Among them, More preferred is 1-methylimidazole.

The basic catalyst preferably contains 0 to 0.5 mol per 1 mol of the cationically polymerizable cyclic ether compound having the polymerizable double bond. More preferably 0 to 0.2 mol.

1-9. Polymerization inhibitor

In the synthesis of the polyester amide acid (A), other raw materials other than the above may be included as necessary as long as the raw materials do not impair the purpose of the present invention. Examples of other raw materials include polymerization inhibitors.

Specific examples of the polymerization inhibitor to be used in the present invention include hydroquinone, methylhydroquinone, 4-methoxyphenol and dibutylhydroxytoluene, among which 4-methoxyphenol used in the examples is more preferable .

The polymerization inhibitor preferably contains 0 to 0.1 mol per 1 mol of the cationically polymerizable cyclic ether compound having a polymerizable double bond. More preferably 0 to 0.05 mol.

1-10. The solvent used for the synthesis reaction of the polyester amide acid (A)

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amide acid (A) include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (hereinafter abbreviated as EDM), diethylene glycol diethyl Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter may be abbreviated as PGMEA), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, lactic acid Ethyl, 3-methoxybutyl acetate (hereinafter abbreviated as MBA), and cyclohexanone. Of these, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, or diethylene glycol methyl ethyl ether are preferable.

1-11. Synthesis method of polyester amide acid (A)

The polyester amide acid (A) of the present invention is synthesized as follows. In the presence of a solvent, a liquid composition of an intermediate polymer is obtained by reacting X mole of tetracarboxylic dianhydride, Z mole of polyhydric hydroxy compound, and W mole of polymerizable double bond-containing cationic polymerizable cyclic ether compound Then, Y mol of diamine is reacted.

In the case of using a compound having three or more acid anhydride groups in addition to the raw materials, it is preferable to use X-mole of tetracarboxylic dianhydride, compound having three or more V-mole of acid anhydride groups, Z- And a cationic polymerizable cyclic ether compound having a polymerizable double bond of W mol are reacted to obtain a liquid composition of an intermediate polymer, followed by reacting with Y mol of diamine.

When a monohydroxy compound is used in addition to the raw material, X mol of a tetracarboxylic dianhydride, Z mol of a polyhydroxy compound and a monohydroxy compound, and W mol of a polymerizable double bond Is reacted to obtain a liquid composition of an intermediate polymer, and then Y mol of diamine is reacted.

When a compound having at least three acid anhydride groups and a monohydroxy compound are used in addition to the raw material, it is preferable to use X mole of a tetracarboxylic acid dianhydride, a compound having three or more V moles of acid anhydride groups, Z mol of a polyhydric hydroxy compound, a monohydroxy compound, and a W-mole polymerizable double bond-containing cationic polymerizable cyclic ether compound to obtain a liquid composition of an intermediate polymer, followed by reacting with Y mol of diamine.

In the case of synthesizing by the above four methods, the first step of obtaining the intermediate polymer is preferably carried out at 40 to 200 ° C for 0.2 to 20 hours, and the second step of reacting the intermediate polymer with the diamine is performed at 0.1 to 0.1 It is recommended to react for ~ 6 hours.

The polyester amide acid (A) of the present invention may be polymerized as follows. X mol of a tetracarboxylic dianhydride and Z mol of a polyhydric hydroxy compound are reacted in the presence of a solvent to obtain a liquid composition of an intermediate polymer and then reacted with Y mol of diamine to obtain a polyester amide acid, W mole of a polymerizable double bond is reacted with a cationically polymerizable cyclic ether compound having a polymerizable double bond.

In the case of using a compound having three or more acid anhydride groups in addition to the raw materials, it is preferable to use X-mole of tetracarboxylic dianhydride, compound having three or more V-mole of acid anhydride groups, Z- A compound is reacted to obtain a liquid composition of an intermediate polymer, and then Y diamine is reacted to obtain a polyester amide acid, and a cationic polymerizable cyclic ether compound having a polymerizable double bond of W mole is reacted therewith.

When a monohydroxy compound is used in addition to the raw material, X mol of a tetracarboxylic dianhydride, Z mol of a polyhydric hydroxy compound and a monohydroxy compound are reacted in the presence of a solvent to obtain a liquid composition of an intermediate polymer Then, Y diamine diamine is reacted to obtain a polyester amide acid, and a cationic polymerizable cyclic ether compound having a polymerizable double bond of W mole is reacted therewith.

When a compound having three or more acid anhydride groups and a monohydroxy compound in addition to the raw material are used, X mole of a tetracarboxylic acid dianhydride, a compound having three or more V mole anhydride groups, Z A molar polyhydric hydroxy compound and a monohydroxy compound are reacted to obtain a liquid composition of an intermediate polymer and then reacted with Y mol of diamine to obtain a polyester amide acid, The polymerizable cyclic ether compound is reacted.

In the case of synthesizing by the above four methods, the first step of obtaining the intermediate polymer is preferably carried out at 40 to 200 ° C for 0.2 to 20 hours, and the second step of reacting the intermediate polymer with the diamine is performed at 0.1 to 0.1 For 6 hours. In the third step of reacting the cationically polymerizable cyclic ether compound having a polymerizable double bond, the reaction may be carried out at 10 to 150 캜 for 0.2 to 20 hours.

When the polymerization is carried out by the above-described methods, the basic catalyst or polymerization inhibitor may be added as occasion demands.

When a cationically polymerizable cyclic ether compound having a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, and a polymerizable double bond is used in a raw material, X, Y, Z, 1), the formula (2) and the formula (3). Within this range, the solubility of the polyester amide acid in a solvent is high, and the applicability of the photosensitive composition is improved.

In the formula (1), preferably 0.7? Z / Y? 7.0, and 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. In the formula (3), it is preferable that 0.05? W / 2X? 1.0, and more preferably 0.1? W / 2X? 0.5.

The case of using a monohydroxy compound in addition to the raw material is also the same as the above.

When a tetracarboxylic acid dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond are used in a raw material, It is preferable that Z and W are defined by the ratio in which the relation of the above-mentioned formula (1), formula (2) and formula (3 ') is established between them. Within this range, the solubility of the polyester amide acid in a solvent is high, and the applicability of the photosensitive composition is improved.

In the formula (1), preferably 0.7? Z / Y? 7.0, and 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. In the formula (3 '), it is preferable that 0.05? W / (2X + rV)? 1.0 and more preferably 0.1? W / (2X + rV)? 0.5.

The case of using a monohydroxy compound in addition to the raw material is also the same as the above.

When the reaction solvent is used in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, the polyhydroxy compound, and the cationically polymerizable cyclic ether compound having a polymerizable group, Do. When a compound having three or more acid anhydride groups in addition to the above essential raw material compounds is used, a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, a cationically polymerizable cyclic ether compound having a polymerizable group and an acid anhydride group It is preferable to use a reaction solvent in an amount of 100 parts by weight or more based on 100 parts by weight of the total amount of the compounds having three or more. When a monohydroxy compound is used in addition to the above essential raw material compound, a total amount of tetracarboxylic acid dianhydride, diamine, polyhydric hydroxy compound, cationically polymerizable cyclic ether compound having a polymerizable group and monohydroxy compound is 100 It is preferable to use a reaction solvent in an amount of 100 parts by weight or more based on parts by weight. When a compound having at least three acid anhydride groups and a monohydroxy compound are used in addition to the above essential raw material compounds, a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, a cationically polymerizable cyclic compound having a polymerizable group It is preferable to use a reaction solvent in an amount of 100 parts by weight or more based on 100 parts by weight of the total of the ether compound, the compound having three or more acid anhydride groups, and the monohydroxy compound.

The polyester amide acid (A) synthesized by using a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound and a cationically polymerizable cyclic ether compound having a polymerizable double bond in a raw material has a structure represented by the formula (4) Unit and a constituent unit represented by the formula (5), and the terminal thereof is derived from a tetracarboxylic acid dianhydride, a diamine, a polyhydric hydroxy compound, or a cationically polymerizable cyclic ether compound having a polymerizable double bond , An acid anhydride group, an amino group, a hydroxyl group, a polymerizable double bond, or a monovalent organic group, or an additive other than these compounds. By including such a constitution, the curability is improved.

The polyester amide acid (A) synthesized by using a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, a cationically polymerizable cyclic ether compound having a polymerizable double bond, and a monohydroxy compound as raw materials can be produced by reacting a A structural unit represented by the formula (4), a structural unit represented by the formula (5) and a structural unit represented by the formula (6), and the terminal thereof may be an acid anhydride group, an amino group, An organic group or a monohydric group derived from a monohydroxy compound, or an additive other than these compounds. By including such a constitution, the curability is improved, and the storage stability of the photosensitive composition is improved as described above.

A polyester amide acid (A) synthesized using a tetracarboxylic acid dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond as raw materials ) Includes a constituent unit represented by the formula (4) and a constituent unit represented by the formula (5), and the terminal thereof is a monovalent group derived from a compound having three or more acid anhydride groups and acid anhydride groups, A polymerizable double bond, or a monovalent organic group, or an additive other than these compounds. By including such a constitution, the transparency of the cured film is improved as described above.

A tetracarboxylic acid dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydric hydroxy compound, a cationically polymerizable cyclic ether compound having a polymerizable double bond, and a poly The ester amide acid (A) contains the constituent unit represented by the formula (4), the constituent unit represented by the formula (5) and the constituent unit represented by the formula (6), and the terminal thereof is bonded to the acid anhydride group, An amino group, a hydroxyl group, a polymerizable double bond, a monovalent organic group, or an additive other than these compounds. By including such a structure, the transparency of the cured film is improved as described above, and the storage stability of the photosensitive composition is improved.

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

The weight average molecular weight in the present specification is a value in terms of polystyrene determined by the GPC method (column temperature: 35 캜, flow rate: 1 ml / min). As the standard polystyrene, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 from Agilent Technologies, Inc.), PLgel MIXED-D (Agilent Technologies Co.) . &Lt; / RTI &gt; The weight average molecular weights of commercially available products in this specification are catalog published values.

2. Photosensitive composition

The photosensitive composition according to the embodiment of the present invention includes a polyester amide acid (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), an epoxy compound (D), and an additive (E) .

2-1. The polyester amide acid (A) having a polymerizable double bond

The polyester amide acid (A) having a polymerizable double bond used in the photosensitive composition is the polyester amide acid (A) described above.

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

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

The compound (B) having a polymerizable double bond used in the photosensitive composition is a compound having a polymerizable double bond other than the polyester amide acid (A). The compound (B) having a polymerizable double bond is not particularly limited, except that it is other than the polyester amide acid (A), but a compound having two or more polymerizable double bonds per molecule is preferable.

When the compound (B) having a polymerizable double bond is contained in an amount of 50 to 300 parts by weight based on 100 parts by weight of the polyester amide acid (A), the residual film ratio after development becomes satisfactory.

Examples of the compound having two or more polymerizable double bonds per molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, epichlorohydrin-modified diethylene glycol di (meth) acrylate, epichlorohydrin-modified triethylene (Meth) acrylate, epichlorohydrin-modified tetraethylene glycol di (meth) acrylate, epichlorohydrin modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) (Meth) acrylate, epichlorohydrin-modified propylene glycol di (meth) acrylate, epichlorohydrin-modified dipropylene glycol di (meth) acrylate, epichlorohydrin-modified tripropylene glycol (Meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin-modified polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) (Meth) acrylate, trimethylol propane tri (meth) acrylate, propylene oxide modified trimethylol propane tri (meth) acrylate, epichlorohydrin modified trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (Meth) acrylate, glycerol di (meth) acrylate, (Meth) acrylate, epichlorohydrin denatured glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin denatured 1,6-hexanediol di ) Acrylate, methoxylated cyclohexyldi (meth) acrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (Meth) acrylate, diglycerin tetra (meth) acrylate, diglycerin ethylene oxide modified acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (Meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl-modified dipentaerythritol penta (meth) acrylate, alkyl modified (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, alkyl modified dipentaerythritol tri Modified (meth) acrylate oligomer, allylated cyclohexyldi (meth) acrylate, bis [(meth) acryloxyneopentylglycol] adipate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (Meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F di Di (meth) acrylate, 1,3-butylene glycol (meth) acrylate, dicyclopentanyl diacrylate, polyester diacrylate, poly (Meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, ethylene oxide-modified phosphoric acid di (meth) acrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, (Meth) acrylate, ethylene oxide modified phosphoric acid tri (meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di , Neopentyl glycol modified trimethylol propane di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, isocyanuric acid ethylene oxide modified triacrylate, caprolactone modified tris [(meth) acryloxyethyl] iso Cyanurate, (meth) acrylate isocyanurate, Nyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane (Meth) acrylic acid modified product of a phenol novolak type epoxy resin, a prepolymer, a pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, a dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer, a non-yellowing type oligourethane acrylate, , A (meth) acrylic acid modified product of a cresol novolak type epoxy resin, and a 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 at least one compound selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacryl (Meth) acryloyl oligomer, isocyanuric acid ethylene oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, or a mixture thereof is preferably used in view of heat resistance and chemical resistance of the cured film Do.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polybasic acid modified (meth) acryl oligomer, ethylene isocyanurate As the oxide-modified diacrylate, isocyanuric acid ethylene oxide-modified triacrylate, or a mixture thereof, the following commercially available products can be used.

A specific example of trimethylolpropane triacrylate is ARONIX M-309 (trade name, manufactured by Toagosei Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate include Aronix M-306 (65-70 wt%), M-305 (55-63 wt%), M-303 (Content of pentaerythritol triacrylate in the mixture is in the range of 0.1 to 5% by weight), M-452 (25 to 40% by weight) and M-450 Quot;). 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 (30 to 40% by weight), M-406 (25 to 35% by weight) and M-405 (10 to 20% by weight %) (All trade names; Toagosei Co., Ltd., content in parentheses is the catalog value of the content of dipentaerythritol pentaacrylate in the mixture). Specific examples of the polybasic acid-modified (meth) acryl oligomer include Aronix M-510 and M-520 (all trade names, Toagosei Co., Ltd.). A specific example of the isocyanuric acid ethylene oxide-modified diacrylate is ARONIX M-215 (trade name, manufactured by Toagosei Co., Ltd.). Specific examples of the mixture of isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate include Aronix M-313 (30 to 40 wt%) and M-315 (3 to 13 wt% (All trade names; Toagosei Co., Ltd., content in parentheses is the catalog value of the content of isocyanuric acid ethylene oxide-modified diacrylate in the mixture). A specific example of the acrylic acid-modified product of the phenol novolak type epoxy resin is TEA-100 (trade name, manufactured by KSM). A specific example of the acrylic acid-modified product of the cresol novolak type epoxy resin is CNEA-100 (trade name; manufactured by KSM).

2-2-2. 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 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 1 to 50 parts by weight per 100 parts by weight of the polyester amide acid (A) The resolution is improved.

Examples of the compound having one such polymerizable double bond per molecule and having at least one functional group of -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, phthalic acid 2- (meth) acryloyloxyethyl, phthalic acid 2- (meth) acryloyloxyethyl-2-hydroxyethyl, 4-hydroxyphenyl (meth) acrylate, p-hydroxy (meth) acrylanilide, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, Acrylate, 3- (2-hydroxyphenyl) acrylic acid, and? - Le diplopia ethyl (meth) acrylate.

Among them, 4-hydroxyphenyl (meth) acrylate and p-hydroxy (meth) acrylanilide have good resolution.

2-3. The photopolymerization initiator (C)

The photopolymerization initiator contained in the photosensitive composition is preferably a photopolymerization initiator containing a polyester amide acid (A), a polymerizable double bond-containing compound (B), a photopolymerization initiator (C), an epoxy compound (D) So long as it is capable of initiating polymerization of the composition.

Examples of the photopolymerization initiator contained in the photosensitive composition include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2-methyl-4-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, 1-hydroxycyclohexyl phenyl ketone, , Isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-benzyl-2-dimethylamino-1- (4-morpholino) thiophene-1-one (trade name; IRGACURE 907, BASF Japan K.K.) (Trade name: IRGACURE 369, BASF Japan K.K.), ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, 4,4'-di - Butyl per (Phenylthio) phenyl] -2- (O (phenylthio) carbonyl) benzophenone, 3,4,4'-tri -Benzoyloxime) (for example, trade name: IRGACURE OXE01, BASF Japan K.K.), ethanone, 1- [9H-ethyl-6- (2-methylbenzoyl) , IRGACURE OXE03 (trade name, manufactured by BASF Japan K.K.), 1,2-propanedione-1- [4- (4-fluorophenyl) (Trade name; Adeka Aches NCI-930, manufactured by ADEKA Kabushiki Kaisha), adeka (manufactured by Nippon Kayaku Co., Ltd.) Adeka Optomer N-1919 (trade name, ADEKA), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'- (Trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) The Triazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (Trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) (Trichloromethyl) -5- (2 ' -chlorophenyl) -s-triazine, 1, , 3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p- dimethylaminostyryl) benzoxazole, 2- (p- Benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'- Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis 4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2' -Imidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, and bis (η ⁵ -2,4- cyclopentadiene-1-yl) and the like can be mentioned titanium-bis (2,6-di-fluoro-phenyl -3- (1H- pyrrol-1-yl)).

The photopolymerization initiator may be used alone or in combination of two or more. Among the photopolymerization initiators, α-aminoalkylphenone-based, acylphosphine oxide-based and oximeester-based photopolymerization initiators are preferred from the viewpoints of sensitivity of the coating film upon exposure and transparency of the cured film. In the present specification, a thin film obtained by preliminarily drying (prebaking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing, or other methods is referred to as a &quot; coating film &quot;. 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, all the thin films in the steps from the preliminary drying to the drying are referred to as &quot; coating films &quot;, and coatings at any stage of the film formation process are identified by the notation "coating film at the time of exposure" .

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

2-4. The epoxy compound (D)

The epoxy compound (D) used in the photosensitive composition contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding the epoxy compound (D) to the photosensitive composition of the present invention, the heat resistance of the cured film can be enhanced. When the epoxy compound (D) is 20 to 150 parts by weight based on 100 parts by weight of the polyester amide acid (A), the flatness is improved.

As a preferable example of the epoxy compound, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (for example, trade name: Celloxide 2021P, 4- (2-methyloxiranyl) -7-oxabicyclo [4.1.0] heptane (trade name, Celloxide 3000, Propoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxypropoxy) Phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -1- [4- [ 2- [4- [1,1-bis [4 - ([2,3-epoxypropoxy] phenyl) ] Ethyl] phenyl] propane (for example, trade name: TECHMORE VG3101L, manufactured by Showa Denko KK), 1,1,1-tris (4-hydroxyphenyl) ethane triglycidyl ether (trade name: jER 1032H60 , Mitsubishi Kagakuga Bush Triazine-2,4,6 (1H, 3H, 5H) -trione, 2, 3-bis (oxiranylmethyl) (2-oxylanyl) cyclohexane adduct of 2-bis (hydroxymethyl) -1-butanol (for example, trade name EHPE3150, Daicel Corporation), jER YX4000, NC-3000-H, NC-3100 (all trade names, manufactured by Nippon Kayaku Co., Ltd.), and the like .

2-5. The ratio of the polyester amide acid (A), the compound having a polymerizable double bond (B), the photopolymerization initiator (C), and the epoxy compound (D)

In the photosensitive composition, the ratio of the compound (B) having a polymerizable double bond to 100 parts by weight of the polyester amide acid (A) is 20 to 300 parts by weight. When the proportion of the compound (B) having a polymerizable double bond is in this range, the balance between heat resistance, flatness, chemical resistance and residual film ratio after development is good. More preferably, the amount of the compound (B) having a polymerizable double bond is in the range of 100 to 300 parts by weight.

In the photosensitive composition, the proportion of the epoxy compound (D) relative to 100 parts by weight of the polyester amide acid (A) is 20 to 200 parts by weight. When the ratio of the epoxy compound (D) is within this range, the balance between heat resistance and flatness is good. It is more preferable that the epoxy compound (D) is in the range of 20 to 150 parts by weight.

2-6. Additive (E)

Various additives may be added to the photosensitive composition in order to improve coating uniformity, adhesiveness, transparency, resolution, flatness, and chemical resistance. Examples of additives include coupling agents such as anionic, cationic, nonionic, fluorine or silicon leveling agents / surfactants and silane coupling agents, antioxidants such as hindered phenol compounds, hindered amine compounds, phosphorus compounds and sulfur compounds, Modifiers, and epoxy curing agents.

2-6-1. Surfactants

A surfactant may be added to the photosensitive composition in order to improve coating uniformity. Specific examples of the surfactant include Polyflow No.45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (all trade names, Kyoeisha Kagaku Co., Ltd.) Disperbyk 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK-300 , BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK- Surflon-SC-101, Surflon-KH-50, and KF-50-100CS (all trade names, manufactured by Shinetsu Kagaku Kogyo Co., 40, SUPPLENT-S611 (all trade names, manufactured by AGC Seiyaku Chemical Co., Ltd.), Fotogen 222 F, Fotogent 208 G, Fotogen 251, Fotogen 710 FL, Fotogen 710 FM, Fotogen 710 FS, , A printer EFTOP EF-801, EFTOP EF-801 and EFTOP EF-802 (all trade names, manufactured by Mitsubishi Matrix Chemicals Co., Ltd.) MegaPak F-477, MegaPark F-477, MegaPark F-410, MegaPark F-444, MegaPark F-472SF, MegaPark F-477, MegaPark F- 558, Megapack F-559, Megapack F-552, Megapack F-552, Megapack F-553, Megapack F-554, Megapack F-555, Megapack F- TEGO Twin 4100, TEGO Flow (trade name, manufactured by DIC Corporation), &quot; MEGA PARK RS-75, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all trade names, Ebonic Degussa Japan K.K.), fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, Fluoroalkyl ammonium iodide, fluoroalkyl benzoyl ether, (Fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, poly Polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate , Polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene Sorbitan palmitate, polyoxyethylene sorbitan stearate Polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonic acid salts, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

Of these surfactants, BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surplon-S611, , Megafac RS-72-k, Megafarm DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonic acid salts, fluoroalkylsulfonic acid salts such as &lt; RTI ID = 0.0 & At least one selected from the group consisting of a carboxylate, a fluoroalkyl polyoxyethylene ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate is preferable because the coating uniformity of the photosensitive composition is enhanced .

The content of the surfactant in the photosensitive composition is preferably 0.01 to 10 wt% with respect to the total amount of the photosensitive composition.

2-6-2. Coupling agent

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

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples thereof include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Sylla Aces S510 (Trade name: SILA ACE S530, JNC KABUSHIKI KAISHA), 3-mercaptopropyltrimethoxysilane (manufactured by JNC K.K.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (For example, trade name: Silica Ace S810, JNC Ltd.), 3-glycidyloxypropyltrimethoxysilane (for example, trade name: CoatOSil MP200, Momentive Performance Materials, A silane-based coupling agent such as tetrakis (triphenylphosphine)), an aluminum-based coupling agent such as acetalkoxy 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 formed cured film and the substrate is improved.

2-6-3. Antioxidant

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

An antioxidant such as a hindered phenol-based, hindered amine-based, phosphorus-based, or sulfur-based compound may be added to the photosensitive composition. Among them, the hindered phenol system is preferable from the viewpoint of weather resistance. Specific examples include Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (all trade names; BASF Japan whether or ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB AO- . 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.

2-6-4. Molecular weight regulator

The photosensitive composition may further contain a molecular weight regulator to suppress the increase in molecular weight by polymerization and to exhibit excellent resolution. Examples of the molecular weight regulator include mercaptans, xanthogens, quinones, and 2,4-diphenyl-4-methyl-1-pentene.

Specific examples of the molecular weight modifier include 2-hydroxy-1,4-naphthoquinone, benzoquinone, 1,4-naphthoquinone, 1,4-dihydroxynaphthalene, 2,5- Methyl-p-benzoquinone, t-butyl-p-benzoquinone, anthraquinone, n-hexylmercaptane, n-octylmercaptan Dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid, dimethyl xanthogen sulfide, diisopropyl xanthogen disulfide, 2,4-diphenyl-4-methyl-1-pentene, etc. .

The molecular weight modifier may be used alone or in combination of two or more. Among the molecular weight regulators, a naphthoquinone molecular weight regulator is preferable because it exhibits excellent resolution.

Among the molecular weight regulators, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferred from the viewpoint of resolution. It is preferable that the content of the photopolymerization initiator (C) is more than 5.0 times the content of the molecular weight adjuster and that the content of the photopolymerization initiator (C) is less than 30 times from the viewpoint of resolution and that the content of the photopolymerization initiator More preferably not less than 5.1 times and not more than 20 times as much as the content of the component (B). It is more preferable that the content of the photopolymerization initiator (C) is more than 5.2 times and not more than 10 times the content of the molecular weight regulator, and further contains the molecular weight regulator.

2-6-5. Epoxy hardener

The photosensitive composition may further contain an epoxy curing agent to improve flatness and chemical resistance. Examples of the epoxy curing agent include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalyst type curing agents, and thermosensitive acid generators such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts. From the viewpoint of avoiding coloring of the cured film and the heat resistance of the cured film, an acid anhydride-based curing agent or an imidazole-based curing agent is preferable.

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

The ratio of the epoxy curing agent to the epoxy compound (D) is 0.1 to 60 parts by weight of the epoxy curing agent relative to 100 parts by weight of the epoxy compound (D). For example, when the epoxy curing agent is an acid anhydride curing agent, it is preferable to add the carboxylic acid anhydride group or the carboxyl group in an amount of 0.1 to 1.5 times the amount of the epoxy curing agent to the epoxy group. At this time, the carboxylic acid anhydride group is calculated two times. The carboxylic acid anhydride group or the carboxyl group is preferably added in an amount of 0.15 to 0.8 parts by weight, since the chemical resistance is further improved.

2-6-6. Ultraviolet absorber

The photosensitive composition may contain an ultraviolet absorber from the viewpoint of further improving the ability of the patterned transparent film to prevent deterioration.

Specific examples of the ultraviolet absorber are TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names, BASF Japan KK).

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

2-6-7. Anti-aggregation agent

The photosensitive composition may contain an anti-aggregation agent from the viewpoint of fusing a solid component with a solvent to prevent flocculation.

Specific examples of the coagulation inhibitor include Disperbyk-145, Disperfect-161, Disperfect-162, Disperfect-163, Disperfect-164, Disperfect-182, DISPERBAKE-183, DISPERBEAKE-2163, DISPERBEAKE-2164, DISPERBEAKE-2163, DISPERBEAKE-2163, ), FTX-218, Ftergent 710FM, and Ftergent 710FS (all trade names, Neos Co., Ltd.), Flowren G-600 and Flowren G-700 (all trade names, Kyoeisha Kagaku Kogyo Co., Ltd.).

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

2-6-8. Thermal crosslinking agent

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

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

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

2-6-9. Photoacid generator

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

Specific examples of the 1,2-quinonediazide compound include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-tri Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone- -Naphthoquinonediazide-5-sulfonic acid ester, 2,3,3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,3', 4 -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide -5-sulfonic acid ester;

Bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

(P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- (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-naphthoquinone diazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane- 2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

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

Phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4'- [1- [4- [1- [4- hydroxyphenyl] , 4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester;

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5- ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

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

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

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

2-6-10. Other additives

Wherein the photosensitive composition comprises a radically polymerizable compound (P1) represented by the following formula (7), a radically polymerizable compound (P2) having an alkoxysilyl, and a radically polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl (Hereinafter, also referred to as &quot; radical copolymerization polymer &quot;) by radical-copolymerizing the polymer (P3).

Wherein R ⁶ is hydrogen or methyl, R ⁷ to R ¹⁰ are alkyl of 1 to 5 carbon atoms, R ¹¹ is alkyl of 1 to ¹⁰ carbon atoms, m is an integer of 1 to 10, and n Is an integer of 1 to 150.

2-6-10-1. The radical polymerizing compound (P1)

Since the radical polymerizable compound (P1) represented by the formula (7) functions as a surfactant, the use of the (P1) as a raw material enables the radical copolymer polymer to act as a surfactant, Adhesion to a substrate and applicability are improved. By adding the radical polymerizable compound (P1), the radical copolymeric polymer tends to become active on the film surface.

Wherein R ⁶ is hydrogen or methyl, R ⁷ to R ¹⁰ are methyl, R ¹¹ is alkyl of 1 to 10 carbon atoms, m is an integer of 1 to 10, And n is an integer of 1 to 150 are preferable. R ⁶ is methyl, R ⁷ to R ¹⁰ are methyl, R ¹¹ is butyl, m is 3, and n is an integer of 1 to 150, and more preferably n is an integer of 30 to 70, and n is And is particularly preferably an integer of 50 to 70. [ The weight average molecular weight of the radically polymerizable compound (P1) represented by the formula (7) is preferably 500 to 8000.

The radical polymerizable compound (P1) can be produced by a known method. A commercially available product may also be used. For example, FM-0711, FM-0721, and FM-0725 (all trade names, manufactured by JNC Corporation).

2-6-10-2. The radically polymerizable compound (P2) having alkoxysilyl

In the photosensitive composition, a radically polymerizable compound (P2) having alkoxysilyl is used as a raw material for obtaining the radical copolymerization polymer. Preferred radically polymerizable compounds (P2) are 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3 - (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and p-styryltrimethoxysilane. Among them, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane are preferable because of their good flatness. (P2), transparency, chemical resistance and the like are improved. Further, the adhesion with the base material is improved by the silane coupling effect.

2-6-10-3. A radically polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl,

In the photosensitive composition, a radical polymerizable compound (P3) having at least one of epoxy, carboxyl and hydroxyphenyl is used as a raw material for obtaining the radical copolymer polymer. Preferred radical polymerizable compounds (P3) are selected from the group consisting of glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid and 4-hydroxyphenyl vinyl ketone Or more. (P3) functions as a crosslinking agent for the polymer, contributing to improvement of heat resistance, chemical resistance and the like.

2-6-10-4. Method for producing radical copolymerizable polymer

The radical copolymer polymer is obtained by copolymerizing a radical polymerizable compound (P1) represented by the formula (7), a radically polymerizable compound (P2) having an alkoxysilyl and a radically polymerizable compound having at least one of epoxy, carboxyl and hydroxyphenyl P3). &Lt; / RTI &gt; The method of producing the radical copolymerization polymer is not particularly limited, but the radical copolymerization polymer can be prepared by heating the above-mentioned radical polymerizable compounds in the presence of a radical initiator. As the radical initiator, an organic peroxide, an azo compound and the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 to 150 캜. The reaction time is not particularly limited, but is usually in the range of 1 to 48 hours. Further, the reaction can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent used for the radical copolymerization reaction is preferably a solvent in which the resulting polymer dissolves. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxy Ethyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate , Propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, Propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol Methyl ethyl ether. One of these solvents may be used as the solvent, or a mixture of two or more of them may be used.

The radical copolymerization polymer used in the photosensitive composition may be a radical copolymerization polymer solution in which the solvent used for the polymerization is left as it is in consideration of handling property or the like and may be a radical copolymerization polymer in a solid state in consideration of transportability and the like by removing the solvent.

Radical copolymerized polymers are preferred because they have good film-forming properties when the weight average molecular weight determined by GPC analysis using polystyrene as a standard is in the range of 1,000 to 50,000. When the weight-average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is more preferable. When the weight average molecular weight is in the range of 2,500 to 15,000, the flatness and chemical resistance of the cured film are particularly preferable.

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

2-7. solvent

A solvent may be added to the photosensitive composition. The solvent optionally added to the photosensitive composition of the present invention is a solvent which is capable of dissolving the polyester amide acid (A), the compound (B) having a polymerizable double bond, the photopolymerization initiator (C), the epoxy compound desirable. Specific examples of the solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, Methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-hydroxypropionic acid, ethyl 3-hydroxypropionate, methyl 3-hydroxypropionate, methyl 3-methoxypropionate, Methoxypropionate, methyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, Propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl Ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol Methyl ethyl ether. One of these solvents may be used as the solvent, or a mixture of two or more of them may be used.

2-8. Preservation of Photosensitive Compositions

When the photosensitive composition is stored in the range of -30 캜 to 25 캜, the stability of the composition over time is improved. If the storage temperature is -20 占 폚 to 10 占 폚, no precipitates are more preferable.

3. Curing film of photosensitive composition

The photosensitive composition is prepared by mixing a polyester amide acid (A), a compound having a polymerizable double bond (B), a photopolymerization initiator (C), an epoxy compound (D), and an additive (E) And then uniformly mixing and dissolving them. As the additive (E), a coupling agent, a surfactant, and other additives may be selected and used depending on the intended characteristics.

The coated film can be formed by applying the photosensitive composition prepared as described above (after dissolving in a solvent in a solid state without solvent) to the surface of the substrate and removing the solvent, for example, by heating. 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 coated film is heated (prebaked) by a hot plate, an oven or the like. The heating conditions vary depending on the kind of each component and the mixing ratio, but it is usually from 70 to 150 DEG C for 5 to 15 minutes in an oven and from 1 to 5 minutes in a hot plate.

Then, the coating film is irradiated with ultraviolet rays through a mask having 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 alkaline developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon or the like to dissolve and remove an unnecessary portion. 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.

In order to completely cure the coating film at the end, 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.

The cured film obtained in this way is further characterized in that it further comprises: 1) a polyamic acid portion of the polyester amide acid (A) dehydrated to form an imide bond, and 2) the carboxylic acid of the polyester amide acid is an epoxy group- And is therefore 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 imaging element can be manufactured using a color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or a transparent insulating film formed between a transparent electrode and an orientation film, in addition to a protective film for a color filter. Further, the cured film of the present invention is also effective as a protective film for an LED light-emitting body.

Example

Next, the present invention will be described concretely with reference to examples and comparative examples, but the present invention is not limited to these examples at all.

[Synthesis Example 1] Synthesis of polyester amide acid (A1) having a polymerizable double bond

(PGMEA), 1,2,3,4-butanetetracarboxylic acid dianhydride (BT-100) and SMA1000P (trade name: styrene-maleic anhydride) were added to a four-necked flask equipped with a stirrer, Hydroxybutyl acrylate glycidyl ether (4HBAGE) were charged in the following proportions in the following order and stirred at 125 DEG C for 6 hours in a dry nitrogen stream, (Synthetic first step).

PGMEA 43.10g

BT-100 2.52 g

SMA1000P 12.01 g

Benzyl alcohol 3.67 g

4HBAGE 4.24g

Thereafter, the solution after the reaction was cooled to 25 DEG C, 3,3'-diaminodiphenylsulfone (DDS) and PGMEA were added at the following weights, stirred at 20 to 30 DEG C for 2 hours, Followed by stirring for 1 hour (synthetic second step).

DDS 0.79g

PGMEA 6.74 g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.25]

The solution was cooled to room temperature to obtain a 30 wt% solution (A1) of light yellow transparent polyester amide acid. A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 32,300.

[Synthesis Examples 2 to 7] Synthesis of polyester amide acid solutions (A2 to A7)

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

For the names in Table 1, PGMEA is propylene glycol monomethyl ether acetate, ODPA is 4,4'-diphenyl ether tetracarboxylic dianhydride, GMA is glycidyl methacrylate, OXE-30 is (3 -Ethyloxetane-3-yl) methyl methacrylate, respectively.

[Table 1]

[Synthesis Example 8] Synthesis of polyester amide acid (A8) having polymerizable double bond

(PGMEA), 1,2,3,4-butanetetracarboxylic acid dianhydride (BT-100) and SMA1000P (trade name: styrene-maleic anhydride) were added to a four-necked flask equipped with a stirrer, Maleic acid copolymer, Kawahara Yuka Chemical Co., Ltd.) and benzyl alcohol were charged in the order of the following weights, and the mixture was stirred at 125 DEG C for 2 hours in a dry nitrogen stream (synthetic first step).

PGMEA 26.74 g

BT-100 1.91 g

SMA1000P 9.12g

Benzyl alcohol 2.79 g

Thereafter, the solution after the reaction was cooled to 25 DEG C, 3,3'-diaminodiphenylsulfone (DDS) and PGMEA were added at the following weights, stirred at 20 to 30 DEG C for 2 hours, Followed by stirring for 1 hour (synthetic second step).

DDS 0.60g

PGMEA 4.41 g

Thereafter, the solution after the reaction was cooled to 25 DEG C, glycidyl methacrylate (GMA), 1-methylimidazole (NMI) and 4-methoxyphenol (MQ) C for 8 hours (synthetic third step).

GMA 0.51 g

NMI 0.056 g

MQ 0.011 g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.06]

The solution was cooled to room temperature to obtain a 30 wt% solution (A8) of light yellow transparent polyester amide acid. A part of the solution was sampled and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the obtained polymer (A8) had a weight average molecular weight of 14,700.

[Synthesis Examples 9 to 11] Synthesis of polyester amide acid solutions (A9 to A11)

Each component was reacted with the weight (unit: g), temperature and time described in Table 2 in accordance with the method of Example 8 to obtain a polyester amide acid solution.

[Table 2]

[Comparative Synthesis Examples 1 and 2] Synthesis of polyester amide acid solutions (a1 and a2)

Each component was reacted with the weight (unit: g), temperature and time described in Table 3 in accordance with the method of Example 1 to obtain polyester amide acid solutions (a1) and (a2).

[Table 3]

[Comparative Synthesis Example 3] Synthesis of polyester amide acid solution (a3)

(PGMEA), 1,2,3,4-butanetetracarboxylic acid dianhydride (BT-100) and SMA1000P (trade name: styrene-maleic anhydride) were added to a four-necked flask equipped with a stirrer, (GMA), and 3,3'-diaminodiphenylsulfone (DDS) in the following proportions in the order of the weight of the resin (C) And the mixture was stirred at 125 DEG C for 2 hours in a stream of nitrogen.

PGMEA 49.85 g

BT-100 2.66g

SMA1000P 12.66 g

Benzyl alcohol 3.87 g

GMA 3.18g

DDS 0.83g

[Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.25]

White insoluble matter was generated, and a homogeneous solution could not be obtained.

[Comparative Synthesis Example 4] Synthesis of polyester amide acid solution (a4)

Each component was reacted with the weight (unit: g), temperature and time described in Table 4 in accordance with the method of Comparative Example 3, but a uniform solution of the polyester amide acid could not be obtained.

[Table 4]

[Example 1]

A polyester amide acid solution (A1) (a polyester amide acid (A) component) obtained in Synthesis Example 1, U-6LPA (Shin Nakamura Co., (Component (B) having a polymerizable double bond), NCI-930 (ADEKA) (a photopolymerization initiator (C)), VG3101L (an epoxy compound (D) , Trimellitic anhydride (TMA), 3-glycidoxypropyltrimethoxysilane (trade name: SILLAACE S510, JNC KABUSHIKI KAISHA), AO-60 (ADEKA KABUSHIKI), quinoester QE (Unit: g) shown in Table 5-1, and the mixture was stirred at room temperature for 3 hours to give a mixture of the components (A) and (B) And dissolved homogeneously. Subsequently, BYK-342 (BYK Additives & Instruments) was charged, stirred at room temperature for 1 hour, and filtered through a membrane filter (0.2 mu m) to prepare a photosensitive composition.

[Examples 2 to 11]

Each component was mixed with the weight (unit: g) shown in Tables 5-1 and 5-2 in accordance with the method of Example 1 to obtain a photosensitive composition.

[Table 5-1]

In the table, &quot; M-402 &quot; represents a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; Aronix M-402 (Toagosei Co., Ltd.), "RS-72-K" is a surfactant; Megapak RS-72-K (DIC Corporation) (hereinafter the same).

[Table 5-2]

&Quot; M-520 &quot; in the table indicates polybasic acid-modified (meth) acryl oligomer; Aronix M-520 (Toagosei Co., Ltd.) and &quot; EHPE3150 &quot; are 1,2-epoxy-4- (2-oxiranyl) cyclohexane adducts of 2,2-bis (hydroxymethyl) Water; EHPE3150 (Daicel Corporation), &quot; F-556 &quot; is a surfactant; Megapak F-556 (DIC Corporation).

These photosensitive compositions were spin-coated on a glass substrate at 950 rpm for 10 seconds and prebaked on a hot plate at 100 캜 for 80 seconds. Next, the resist film was exposed through an exposure gap of 100 mu m using a proximity photoresist TME-150PRC (trade name, available from Topcon Co., Ltd.) through a mask having holes and line patterns of 50 mu m width in the air. The exposure amount was 30 mJ / cm 2, as measured with a cumulative light amount meter UIT-102 (trade name; manufactured by Ushio Denshiku K.K.) and a light receiving device UVD-365PD (trade name; manufactured by Ushio Denki K.K.). After the exposure, the coated film was developed with an aqueous NaHCO ₃ solution at 27 ° C for 40 seconds, and then the coated film was rinsed with running water (pure water) for 20 seconds. Further, post-baking was performed in an oven at 230 占 폚 for 30 minutes to obtain a glass substrate on which a patterned cured film having a film thickness of 1.5 占 퐉 was formed.

With respect to the cured film thus obtained, the residual film ratio and the resolution after development were evaluated by the following methods. The results are shown in Tables 6-1 and 6-2.

[Evaluation method of residual film ratio after development]

The film thickness before development and the film thickness after development were measured using a step, surface roughness and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.) / Film thickness before development) was calculated. A case where the residual film ratio after development is 80% or more is indicated by?, A case where the residual film ratio after development is 75% or more is indicated by?, And a case where the residual film ratio after development is less than 75% is indicated by X.

Here, the pre-development means "after pre-baking", and after development means "after cleaning and drying".

[Evaluation method of resolution]

The obtained glass substrate on which the transparent body on the pattern was formed was observed with a 1,000-fold optical microscope, and the resolution of the 20 mu m hole pattern was confirmed. &Quot; o &quot; and &quot; x &quot;, respectively.

[Table 6-1]

[Table 6-2]

[Comparative Examples 1 to 4]

Each component was mixed and dissolved in accordance with the method of Example 1 by the weight (unit: g) of Table 7 to obtain a photosensitive composition.

[Table 7]

With respect to the cured film obtained in accordance with the method of Example, the residual film ratio and the resolution after development according to Examples were evaluated. The results are shown in Table 8.

[Table 8]

As is clear from the results shown in Tables 6-1 and 6-2, the cured film using the photosensitive composition containing the polyester amide acid (A) having the polymerizable double bonds of Examples 1 to 11 had a residual film ratio after development It can be seen that the resolution is balanced. On the other hand, as shown in Table 8, all of the cured films using the photosensitive compositions containing the polyester amide acids of Comparative Examples 1 to 4 are inferior in residual film ratio after development.

As described above, a polyester having a polymerizable double bond, which is a reactant of a raw material containing a tetracarboxylic dianhydride, a diamine and a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond as an essential component By using the amide acid (A), the residual film ratio and resolution after development could be satisfied.

Since the cured film obtained from the photosensitive composition of the present invention is excellent in optical characteristics such as heat resistance, transparency, flatness, resolution and residual film ratio, it can be used as a protective film for a color filter, an LED light emitting element, It can also be used as a transparent insulating film formed between the transparent electrode and the alignment film.

Claims (12)

A reaction product of a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyhydric hydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond,
(1), wherein X is a tetra carboxylic acid dianhydride, Y is a diamine, Z is a polyhydric hydroxy compound, and W is a polymerizable double bond. , The formula (2) and the formula (3) are satisfied.
0.2? Z / Y? 8.0 (1)
0.2? (Y + Z) /X? 5.0 (2)
0.05? W / 2? X? 1.0 (3) The reaction product according to claim 1, further comprising a compound having three or more acid anhydride groups,
Among the raw materials, a tetondricarboxylic acid dianhydride of X mole, a diamine of Y mole, a polyhydric hydroxy compound of Z mole, a cationically polymerizable cyclic ether compound having a polymerizable double bond of W mole, and an acid anhydride group of V mole A polyester amide acid (A) comprising a compound having three or more compounds in a ratio that the relation of the following formulas (1), (2) and (3 ') is satisfied;
0.2? Z / Y? 8.0 (1)
0.2? (Y + Z) /X? 5.0 (2)
0.0 &gt; W / (2X + rV) &lt; / RTI &gt;
The compound having three or more acid anhydride groups includes r acid anhydride groups per molecule and is used in an amount of 0.1 to 500 parts by weight based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride, diamine, and polyhydric hydroxy compound. The polyester amide acid (A) according to any one of claims 1 to 5, which comprises a constituent unit represented by the following formula (4) and a constituent unit represented by the formula (5):

Wherein R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, and R ³ is a residue obtained by removing a polyhydric hydroxy compound R &lt; ⁵ &gt; is independently H or a group having a polymerizable double bond, and
R ⁵ in the polyester amide acid (A) is not all H. The polyester amide acid (A) according to claim 1 or 2, further comprising a monohydroxy compound in the raw material. The polyester amide acid (A) according to claim 4, which comprises a constituent unit represented by the following formula (4), a constituent unit represented by the formula (5) and a constituent unit represented by the formula (6);

Wherein R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, R ² is a residue obtained by removing two -NH ₂ from a diamine, and R ³ is a residue obtained by removing a polyhydric hydroxy compound R ⁴ is a residue obtained by removing -OH from the monohydroxy compound, R ⁵ is independently a group having H or a polymerizable double bond, and
R ⁵ in the polyester amide acid (A) is not all H. The curable composition according to claim 1, 2, or 4, wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond has a (meth) acryloxy group,
A polyester amide acid (A) having a glycidyl group or an oxetanyl group. The method of claim 1, 2, or 4, wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacryl Epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m Vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate,
3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) Acrylic acid esters such as 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane and 3- 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (2-methacryloyloxyethyl) oxetane, and 3- (2-methacryloyloxyethyl) -3-ethyloxetane. At least one polyester amide acid (A). The method of claim 1, 2, or 4, wherein the tetracarboxylic dianhydride is 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3', 4,4 '-Diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride , And ethylene glycol bis (anhydrotrimellitate), and at least one compound selected from the group consisting of ethylene glycol bis
The diamine is at least one of 3,3'-diaminodiphenylsulfone and bis [4- (3-aminophenoxy) phenyl] sulfone,
The polyhydric hydroxy compound may be at least one compound selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, Bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, isocyanurate tris (2-hydroxyethyl), 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, And 2- (4-hydroxyphenyl) ethanol. The polyester amide acid (A) is at least one selected from the group consisting of: The polyester amide acid (A) according to Claim 2 or 4, wherein the compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. 5. The method according to claim 4, wherein the monohydroxy compound is at least one selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyloxetane, Amidic acid (A). (A), the polymerizable double bond-containing compound (B), the photopolymerization initiator (C), the epoxy compound (D) and the additive (E) according to any one of claims 1 to 10, &Lt; / RTI &gt; The photosensitive composition according to claim 11, wherein the polyester amide acid (A) has a weight average molecular weight of 1,000 to 200,000.