TW201829552A - 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 ≤ 1.0.

Description

Polyester amidate and photosensitive composition containing same

The present invention relates to a photosensitive polymer and a photosensitive composition containing the photosensitive polymer. The present invention relates to a cured film formed from the photosensitive composition, a color filter using the cured film, an insulating film, a protective film, and the like. Furthermore, this invention relates to the manufacturing method of the said photosensitive polymer.

In the usual manufacturing steps of elements such as display elements, the surface is subjected to chemical treatment or high-temperature heating treatment. In order to prevent deterioration, damage, and deterioration caused by the treatment, a protective film is provided on the surface of the element. The protective film is required to have heat resistance, chemical resistance, adhesion to a substrate, transparency, flatness, and the like, as well as good resolution and residual film rate.

In order to form a protective film, it roughly divides into the case where a thermosetting composition or a photosensitive composition is used. In the case of a thermosetting composition, the amount of volatile components generated at the time of film formation is suppressed and the heat resistance is excellent. However, when a thermosetting composition is used, it is difficult to form a scribe line, and it is necessary to perform a washing step of chips generated when the panel is divided.

On the other hand, when a photosensitive composition is used, a scribing line is easy to form and it is excellent in moldability. Therefore, there is an increasing demand for a photosensitive composition that can be formed into a fine shape (fine patterning) for a protective film forming application.

However, in order to form an excellent fine pattern shape, it is required for the photosensitive composition to have an appropriate balance between the resolution and the residual film rate while maintaining a proper solubility in the developing solution. When the solubility of an unexposed part is improved in order to improve resolution, the solubility of an exposed part will also become high, and a residual film rate will fall. On the other hand, if the solubility of the exposed portion is decreased in order to increase the residual film rate, the solubility of the unexposed portion is also reduced, and the resolution is lowered. That is, the photosensitive composition needs to select an appropriate composition ratio to increase the solubility of the exposed portion and reduce the solubility of the unexposed portion. However, only by adjusting the usual constitutional sensitivity of the alkali-soluble resin, photopolymerization initiator, solvent, and additives It is difficult to achieve a balance between the resolution and the residual film rate of the types and composition ratios of the members of the composition. Therefore, in recent years, research into obtaining a balance between resolvability and residual film rate by introducing a photosensitive group into a polymer serving as a matrix of a composition is being actively conducted.

For example, as shown in Patent Document 1, Patent Document 2, and Patent Document 3, an attempt is being made to develop a photosensitive polymerization in which a polymerizable double bond is introduced into a polyimide precursor to give an appropriate balance between resolution and residual film rate. Thing. However, regarding the photosensitive composition containing these photosensitive polymers, the analytic size that can be implemented is not described in the literature. Moreover, the manufacturing process of the photosensitive polymer is a complicated system, and the usable raw materials are limited due to manufacturing conditions. Etc. There is still room for improvement. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2005-154643 [Patent Literature 2] Japanese Patent Laid-Open No. 2006-291221 [Patent Literature 3] Japanese Patent Laid-Open No. 2006-193691

[Problems to be Solved by the Invention] An object of the present invention is to provide a polyester phosphoamic acid as a constituent component of a photosensitive composition having excellent resolution and residual film rate.

[Technical means to solve the problem] The inventors of the present invention conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that they contain a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationic polymerizable ring having a polymerizable double bond The photosensitive composition of polyester amidate having a state-like ether compound as an essential raw material component, while maintaining appropriate solubility in a developing solution, has excellent balance between resolvability and residual film rate, and completed the present invention. The present invention includes the following configurations.

[1] a polyester amido acid (A), which is a reactant of a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond, wherein In the raw materials, the ratio of the following formula (1), formula (2), and formula (3) is established to include X mole tetracarboxylic dianhydride, Y mole diamine, and Z mole polyhydric hydroxyl group. Compound and a cationically polymerizable cyclic ether compound having a polymerizable double bond. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) 0.05 ≦ W / 2X ≦ 1.0 ········ (3)

[2] The polyester amido acid (A) according to [1], which is a reactant of the raw material further containing a compound having three or more acid anhydride groups, and in the raw material, the following formula (1) The ratios where the relationship of formula (2) and formula (3 ') is established include X mol tetracarboxylic dianhydride, Y mol diamine, Z mol polyhydric hydroxy compound, and W mol's polymerizable bis A cationically polymerizable cyclic ether compound having a bond and a compound having three or more acid anhydride groups. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) 0.05 ≦ W / (2X + rV) ≦ 1.0 ····· (3 ') The compound having three or more acid anhydride groups includes r acid anhydride groups in each molecule, and is relative to tetracarboxylic dianhydride, diamine, and polyhydroxy compound. The total amount is 100 parts by weight, and the compound having three or more acid anhydride groups is used in an amount of 0.1 to 500 parts by weight.

[3] The polyester amidine (A) according to [1] or [2], which includes a structural unit represented by the following formula (4) and a structural unit represented by the formula (5). In the formula, 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 from a polyhydric hydroxy compound obtained by removing two -OH residue, R ⁵ is independently H or a group having a polymerizable double bond, and the polyester acid amide (a) is R ⁵ are not all H .

[4] The polyester amido acid (A) according to [1] or [2], wherein the raw material further contains a monohydroxy compound.

[5] The polyester glutamic acid (A) according to [4], which includes a structural unit represented by the following formula (4), a structural unit represented by the formula (5), and a component represented by the formula (6) Building unit. The formula, R ¹ is a tetracarboxylic dianhydride was removed from the two -CO-O-CO- residue formed, R ² is -NH 2 is removed from a diamine residue obtained by _2, R ³ Is a residue obtained by removing 2 -OH from a polyhydroxy compound, R ⁴ is a residue obtained by removing -OH from a monohydroxy compound, R ^{5 is} independently H or a group having a polymerizable double bond, and Not all R ⁵ in the polyester amidine (A) is H.

[6] The polyester amido acid (A) according to [1], [2], or [4], wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond has (meth) acrylic acid Oxy and has glycidyl or oxetanyl.

[7] The polyester amido acid (A) according to [1], [2], or [4], wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond is selected from glycidyl acrylate , Glycidyl methacrylate, 2-methyl glycidyl methacrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6, acrylic acid, 7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methyl 3,4-epoxycyclohexyl methyl acrylate, 3- (propenyloxymethyl) oxetane, 3- (propenyloxymethyl) -2-methyloxa Cyclobutane, 3- (propenyloxymethyl) -3-ethyloxetane, 3- (propenyloxymethyl) -2-phenyloxetane, 3- Acrylates such as (2-propenyloxyethyl) oxetane, 3- (2-propenyloxyethyl) -3-ethyloxetane, etc., 3- (methyl Allyloxymethyl) oxetane, 3- (methacryloxymethyl) -2-methyloxetane, 3- (methylpropane) Alkenyloxymethyl) -3-ethyloxetane, 3- (methacrylmethyloxymethyl) -2-phenyloxetane, 3- (2-methyl At least one of the group consisting of propenyloxyethyl) oxetane and 3- (2-methylpropenyloxyethyl) -3-ethyloxetane.

[8] The polyester amidine (A) according to [1], [2], or [4], wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4,4'-diphenyl Hydrazone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride At least one compound in the group consisting of 1,1,2,3,4-butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate), the diamine is 3,3'- At least one of diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene, the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4 , 4'-Dihydroxydicyclohexyl, tris (2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) ethanol At least one of the group.

[9] The polyester amido 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 polyester amido acid (A) according to [4], wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl At least one of the group consisting of oxetane.

[11] A photosensitive composition comprising the polyester amidate (A) according to any one of [1] to [10], a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C), epoxy compound (D) and additives (E).

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

The polyester amido acid according to the embodiment of the present invention can form a photosensitive composition having excellent heat resistance, transparency, flatness, resolvability, and residual film rate by introducing a polymerizable double bond. The cured film formed using the photosensitive composition can be applied to various applications such as a color filter, a protective film, and an insulating film.

1. Polyesteramine (A) The polyesteramine (A) according to the embodiment of the present invention is a cationically polymerizable ring containing a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a polymerizable double bond. Reactant of the raw material of the ether compound. In addition, the raw materials include X mol tetracarboxylic dianhydride, Y mol diamine, and Z mol in such a ratio that the relationship of the following formula (1), formula (2), and formula (3) is established. Polyhydric hydroxy compound and mol polymerizable cation polymerizable cyclic ether compound having a double bond. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) 0.05 ≦ W / 2X ≦ 1.0 ········ (3)

In addition, in this specification, the said polyester amidate (A) may be expressed as "polyester amidate (A) which has a polymerizable double bond", in order to compare with other materials used together. Make its structural characteristics clear.

The polyester amido acid (A) may be a reactant of the raw material further containing a compound having three or more acid anhydride groups. In this case, the ratio of the following formula (1), formula (2), and formula (3 ') in the raw material includes X mol tetracarboxylic dianhydride, Y mol diamine, Z Mol's polyhydric hydroxy compound, W Mol's cationically polymerizable cyclic ether compound having a polymerizable double bond, and V Mol's compound having three or more acid anhydride groups. 0.2 ≦ Z / Y ≦ 8.0 (1) 0.2 ≦ (Y + Z) /X≦5.0 (2) 0.05 ≦ W / (2X + rV) ≦ 1.0 ····· (3 ')

The compound having three or more acid anhydride groups contains r acid anhydride groups per molecule, and is used in an amount of 0.1 to 300 parts by weight relative to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound. Parts of the compound having three or more acid anhydride groups.

The polyester amidine (A) has a structural unit represented by the following formula (4) and a structural unit represented by the formula (5). The formula, R ¹ is a tetracarboxylic dianhydride was removed from the two -CO-O-CO- residue formed, R ² is -NH 2 is removed from a diamine residue obtained by _2, R ³ It is a residue obtained by removing two -OH from a polyhydroxy compound, and R ^{5 is} independently H or a group having a polymerizable double bond. Further, not all R ⁵ in the polyester amidine (A) is H.

The polyester amidine (A) according to another embodiment of the present invention is a reactant of the raw material further containing a monohydroxy compound. In this case, the compound having three or more acid anhydride groups may or may not be included in the raw material. The polyester amidine (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). In the formula, 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 R ⁴ is a residue obtained by removing two -OH groups from a polyhydroxy compound, R ⁴ is a residue obtained by removing -OH groups from a monohydroxy compound, and R ^{5 is} independently H or a group having a polymerizable double bond. Further, not all R ⁵ in the polyester amidine (A) is H.

At least a solvent is required for the synthesis of the polyester amidate (A) according to the embodiment of the present invention. The solvent can be left directly to form a liquid or gel-like photosensitive composition in consideration of handling properties, and the solvent can be removed to form a solid-state photosensitive property considering handling properties and the like.组合 物。 Composition.

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

1-1. Tetracarboxylic dianhydride In the present invention, a tetracarboxylic dianhydride is used as a material to obtain a polyester amidate (A). Specific examples of the tetracarboxylic dianhydride are preferably 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter sometimes referred to as ODPA), 1,2,3,4- Butanetetracarboxylic dianhydride (hereinafter sometimes referred to as BT-100).

As the tetracarboxylic dianhydride that can be used in the present invention, in addition to the compound, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3, 3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic acid Dianhydride, 2,2 ', 3,3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3', 4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 2,2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid Dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, ethylene glycol bis (anhydrotrimellitic acid ester) (Trade name: TMEG-100, Shinnippon Physico Chemical Corporation) Co., Ltd.), cyclobutanetetracarboxylic dianhydride, methylcyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, ethanetetracarboxylic dianhydride and As the butane tetracarboxylic dianhydride, at least one of the tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, the tetracarboxylic dianhydride that provides good transparency to the cured film is 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4 '-Diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride And TMEG-100, preferably 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic dianhydride and 1,2 , 3,4-butanetetracarboxylic dianhydride.

1-2. Diamine In the present invention, a diamine is used as a material for obtaining polyester amido acid (A). Specific examples of the diamine include 3,3'-diaminodiphenylphosphonium (hereinafter sometimes referred to as DDS) used in the examples.

Specific examples of the diamine usable in the present invention include, in addition to the compounds, 4,4'-diaminodiphenylphosphonium, 3,4'-diaminodiphenylphosphonium, and bis [ 4- (4-aminophenoxy) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [3- (4-aminophenoxy) phenyl]碸, [4- (4-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] 碸, [4- (3-aminophenoxy) phenyl] [ 3- (4-aminophenoxy) phenyl] fluorene and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, at least one of the diamines can be used .

Among these diamines, 3,3'-diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene are preferred from the viewpoint of imparting good transparency to the cured film. , More preferably 3,3'-diaminodiphenylphosphonium.

1-3. Polyhydric hydroxy compound In the present invention, a polyhydric hydroxy compound is used as a material to obtain polyester amidate (A). Specific examples of the polyhydroxy compound are preferably 1,4-butanediol used in the examples.

Examples of the polyhydric hydroxy compound that can be used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol having a weight average molecular weight of 1,000 or less in addition to the compounds described above. Alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol with a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,2-pentanediol, 1,5 -Pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2 1,6-hexanetriol, 1,2-heptanediol, 1,7-heptanediol, 1,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3 1,6-octanediol, 1,2,8-octantriol, 1,2-nonanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol , 1,10-decanediol, 1,2,10-decanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylolpropane, pentaerythritol, diamine Pentaerythritol, tris (2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol S (bis (4-hydroxyphenyl) fluorene), Bisphenol F (bis (4-hydroxyphenyl) methane), 2,2-bis (4-hydroxycyclohexyl) propane 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethanol, diethanolamine, and triethanolamine can be used in the polyhydroxy compound At least one.

Among these polyhydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol Alcohol, tris (2-hydroxyethyl) isocyanurate, 2,2-bis (4-hydroxycyclohexyl) propane, 4,4'-dihydroxydicyclohexyl, 2-hydroxybenzyl alcohol, 4- Hydroxybenzyl alcohol and 2- (4-hydroxyphenyl) ethanol are preferable because they have good solubility in a reaction solvent.

1-4. Cationic polymerizable cyclic ether compound having a polymerizable double bond In the present invention, a cationically polymerizable cyclic ether having a polymerizable double bond is used as a material to obtain polyester amidate (A). Compound. The cationically polymerizable cyclic ether compound having a polymerizable double bond is a compound having a (meth) acryloxy group and a glycidyl group or an oxetanyl group. Specific examples of the cationically polymerizable cyclic ether compound having a polymerizable double bond include glycidyl methacrylate (hereinafter sometimes referred to as GMA) and 4-hydroxybutyl acrylate shrink used in the examples. Glyceryl ether (hereinafter sometimes referred to as 4HBAGE).

Specific examples of the cationically polymerizable cyclic ether compound having a polymerizable double bond that can be used in the present invention include, in addition to the compounds, glycidyl acrylate, glycidyl methacrylate, and methacrylic acid- 2-methylglycidyl ester, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid- 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate Methyl ester, 3- (propenyloxymethyl) oxetane, 3- (propenyloxymethyl) -2-methyloxetane, 3- (propenyloxymethyl) (Methyl) -3-ethyloxetane, 3- (propenyloxymethyl) -2-phenyloxetane, 3- (2-propenyloxyethyl) oxy Acrylates such as heterocyclobutane, 3- (2-propenyloxyethyl) -3-ethyloxetane, and 3- (methacrylomethyloxymethyl) oxetane Alkane, 3- (methacrylfluorenyloxymethyl) -2-methyloxetane, 3- (formyl Allyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methyl Acrylic fluorenyloxyethyl) oxetane and 3- (2-methylpropenyloxyethyl) -3-ethyloxetane may be used in at least one of these specific examples.

1-5. Compound having three or more acid anhydride groups In the present invention, as a material for obtaining polyester amido acid (A), a compound having three or more acid anhydride groups can be used. This is preferable because the transparency of the cured film is improved. The compound having three or more acid anhydride groups contains r acid anhydride groups per molecule, and r is 3 to 50, preferably 3 to 25, and more preferably 5 to 10.

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

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all are trade names; Sichuan Crude Chemical Co., Ltd.). Among these specific examples, SMA1000P having good heat resistance and alkali resistance of the cured film is particularly preferred.

The styrene-maleic anhydride copolymer preferably contains 0.1 to 500 parts by weight based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, and polyhydroxy compound. It is more preferably 10 to 300 parts by weight.

1-6. Monohydroxy compound In the present invention, as a material for obtaining polyester amido acid (A), a monohydroxy compound can be used. When a monohydroxy compound is used, the storage stability of the photosensitive composition is improved.

As a specific example of the said monohydroxy compound, the benzyl alcohol used by the Example is mentioned preferably.

Examples of the monohydroxy compound usable in the present invention include isopropyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and ethylene glycol monoethyl ether in addition to the compounds described above. , Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, 3-ethyl-3-hydroxymethyloxetane, and dimethylbenzyl Methyl alcohol (dimethyl benzyl carbinol).

Among these monohydroxy compounds, benzyl alcohol is particularly preferably used in consideration of the applicability on a color filter when formed into a photosensitive composition.

The reaction is preferably performed with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyhydroxy compound, containing 0 to 300 parts by weight of the monohydroxy compound. It is more preferably 5 to 200 parts by weight.

1-7. Monoamines having an alkoxysilyl group In the synthesis of the polyester amidinic acid (A) of the present invention, it is also possible to include other than those described above, as long as the object of the present invention is not impaired. Other raw materials are used as raw materials, and examples of other raw materials include monoamines having an alkoxysilyl group.

Specific examples of the monoamine having an alkoxysilyl group used in the present invention are preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, Aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4 -Aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-aminophenylmethyldimethoxysilane, p-aminophenyl Methyldiethoxysilane, m-aminophenyltrimethoxysilane and m-aminophenylmethyldiethoxysilane. At least one of these specific examples can be used.

Among these specific examples, 3-aminopropyltriethoxysilane and p-aminophenyltrimethoxysilane, which are excellent in acid resistance of the cured film, are more preferred. From the viewpoint of acid resistance and compatibility, they are particularly preferred. Preferred is 3-aminopropyltriethoxysilane.

It is preferably 0 to 300 parts by weight of a monoamine having an alkoxysilyl group with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyhydroxy compound, and more preferably It is 5 to 200 parts by weight.

Under the condition that X is excessively used with respect to Y + Z within the range of the formula (2), in order to react with an acid anhydride group at the molecular terminal to introduce a silane group at the terminal, a monoamine having an alkoxysilyl group may be added . When a photosensitive composition containing a polyester amidate (A) is used, the acid resistance of the cured film is improved, which is obtained by adding a monoamine having an alkoxysilyl group.

1-8. In the synthesis of polyester amidine (A), basic catalysts may contain other raw materials other than those mentioned above as raw materials, as long as they do not impair the object of the present invention. Examples include basic catalysts.

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

It is preferable that the basic catalyst contains 0 mole to 0.5 mole with respect to 1 mole of the cationic polymerizable cyclic ether compound having a polymerizable double bond. More preferably, it is 0 to 0.2 mol.

1-9. Polymerization inhibitors In the synthesis of polyester glutamic acid (A), as long as the purpose of the present invention is not impaired, other raw materials other than those mentioned above may be included as raw materials, as other raw materials. Examples include polymerization inhibitors.

Specific examples of the polymerization inhibitor used in the present invention include hydroquinone, methylhydroquinone, 4-methoxyphenol, and dibutylhydroxytoluene. Among them, the 4-hydroxybenzene used in the examples is more preferred. Methoxyphenol.

It is preferable that the polymerization inhibitor contains 0 mol to 0.1 mol with respect to 1 mol of the cationically polymerizable cyclic ether compound having a polymerizable double bond. More preferably, it is 0 to 0.05 mol.

1-10. Solvents used in the synthesis reaction of polyester amidate (A) As specific examples of the solvents used in the synthesis reaction of polyester amidate (A), diethylene glycol can be cited: Dimethyl ether, diethylene glycol methyl ethyl ether (hereinafter sometimes referred to as EDM), diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether acetate (hereinafter sometimes referred to as PGMEA), methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, 3-methoxybutyl acetate (hereinafter Sometimes referred to as MBA), cyclohexanone. Among these specific examples, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, or diethylene glycol methylethyl ether is preferred.

1-11. Method for synthesizing polyester amidine (A) The polyester amidine (A) of the present invention is synthesized in the following manner. In the presence of a solvent, an X-mole tetracarboxylic dianhydride, a Z-mole polyhydric hydroxy compound, and a W-mole cationically polymerizable cyclic ether compound having a polymerizable double bond are reacted to obtain an intermediate polymer. The liquid composition was then reacted with Y mole's diamine.

When a compound having three or more acid anhydride groups is further used in the raw material, in the presence of a solvent, X mol tetracarboxylic dianhydride, V mol compound having three or more acid anhydride groups, and Z mol are used. The polyhydric hydroxy compound and the cationically polymerizable cyclic ether compound having a polymerizable double bond of Moore are reacted to obtain a liquid composition as an intermediate polymer, and then reacted with Y Moore's diamine.

When a monohydroxy compound is further used in the raw material, in the presence of a solvent, a polymerizable double bond having X mol tetracarboxylic dianhydride, Z mol polyhydric hydroxy compound, and a mono hydroxy compound and W mol is allowed The cationically polymerizable cyclic ether compound is reacted to obtain a liquid composition as an intermediate polymer, and then reacted with Y mole's diamine.

When a compound having three or more acid anhydride groups and a monohydroxy compound are further used in the raw material, in the presence of a solvent, X mol tetracarboxylic dianhydride and V mol compound having three or more acid anhydride groups are used. Z Mol's polyhydroxy compound reacts with a monohydroxy compound and W Mol's cationically polymerizable cyclic ether compound with a polymerizable double bond to obtain a liquid composition as an intermediate polymer, and then reacts with Y Mol's Amine reaction.

In the case of using the four methods for synthesis, the first step of obtaining the intermediate polymer can be reacted at 40 ° C to 200 ° C for 0.2 hours to 20 hours, and the second step of reacting the intermediate polymer with the diamine can be performed at The reaction is performed at 20 ° C to 150 ° C for 0.1 to 6 hours.

In addition, the polyester amido acid (A) of the present invention can be polymerized in the following manner. In the presence of a solvent, X mole's tetracarboxylic dianhydride and Z mole's polyhydroxy compound are reacted to obtain a liquid composition as an intermediate polymer, and then reacted with Y mole's diamine to obtain a polyester Amidine is made to react with the polyester amidate and a cationically polymerizable cyclic ether compound having a polymerizable double bond.

When a compound having three or more acid anhydride groups is further used in the raw material, in the presence of a solvent, X mol tetracarboxylic dianhydride, V mol compound having three or more acid anhydride groups, and Z mol are used. The polyhydric hydroxy compound is reacted to obtain a liquid composition as an intermediate polymer, and then reacted with Y mole's diamine to obtain polyester amidate, and the polyester amidate is polymerized with W amore The cationically polymerizable cyclic ether compound of the double bond is reacted.

When a monohydroxy compound is further used in the raw material, in the presence of a solvent, a X mol tetracarboxylic dianhydride and a Z mol polyhydric hydroxy compound are reacted with the mono hydroxy compound to obtain a liquid as an intermediate polymer. The composition is then reacted with Y Mol's diamine to obtain polyester amidate, and the polyester amidate is reacted with a Wmol's cationically polymerizable cyclic ether compound having a polymerizable double bond.

When a compound having three or more acid anhydride groups and a monohydroxy compound are further used in the raw material, in the presence of a solvent, X mol tetracarboxylic dianhydride and V mol compound having three or more acid anhydride groups are used. Z Mol's polyhydric hydroxyl compound reacts with a monohydroxy compound to obtain a liquid composition as an intermediate polymer, and then reacts with Y Mol's diamine to obtain a polyester amidate, and the polyester amidate The acid reacts with a cationically polymerizable cyclic ether compound having a polymerizable double bond.

In the case of using the four methods for synthesis, the first step of obtaining the intermediate polymer can be reacted at 40 ° C to 200 ° C for 0.2 hours to 20 hours, and the second step of reacting the intermediate polymer with the diamine can be performed at The reaction is performed at 20 ° C to 150 ° C for 0.1 hour to 6 hours, and the third step of reacting the cationic polymerizable cyclic ether compound having a polymerizable double bond can be reacted at 10 ° C to 150 ° C for 0.2 hours to 20 hours.

When polymerization is performed by each of the methods, the basic catalyst or the polymerization inhibitor may be added as appropriate.

When a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond are used in the raw material and reacted, it is preferable to use X, Y, Z, and W The ratio of the relationship between the formulas (1), (2), and (3) is established to determine the X, Y, Z, and W. If it is the said range, the solubility of polyester amidine in a solvent will become high, and the coating property of a photosensitive composition will improve.

In the formula (1), 0.7 ≦ Z / Y ≦ 7.0 is preferable, and 1.0 ≦ Z / Y ≦ 5.0 is more preferable. In the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferred, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferred. In the formula (3), 0.05 ≦ W / 2X ≦ 1.0 is preferred, and 0.1 ≦ W / 2X ≦ 0.5 is more preferred. In the case where a monohydroxy compound is further used in the raw material, it is also the case described above.

When a tetracarboxylic dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond are used in a raw material for reaction, it is preferably The X, Y, Z, and W are determined at a ratio at which the relationships of the formulas (1), (2), and (3 ′) are established between X, Y, Z, and W. If it is the said range, the solubility of polyester amidine in a solvent will become high, and the coating property of a photosensitive composition will improve.

In the formula (1), 0.7 ≦ Z / Y ≦ 7.0 is preferable, and 1.0 ≦ Z / Y ≦ 5.0 is more preferable. In the formula (2), 0.5 ≦ (Y + Z) /X≦4.0 is preferred, and 0.6 ≦ (Y + Z) /X≦2.0 is more preferred. In the formula (3 ′), 0.05 ≦ W / (2X + rV) ≦ 1.0 is preferred, and 0.1 ≦ W / (2X + rV) ≦ 0.5 is more preferred. In the case where a monohydroxy compound is further used in the raw material, it is also the case described above.

The reaction proceeds smoothly when 100 parts by weight or more of the reaction solvent is used with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, diamine, polyhydroxy compound, and cationically polymerizable cyclic ether compound having a polymerizable group. Therefore, it is preferable. When a compound having three or more acid anhydride groups is further used as the required raw material compound, it is preferably a cationically polymerizable cyclic ether compound having a polymerizable group with respect to tetracarboxylic dianhydride, diamine, polyhydroxy compound, and polymerizable group. And a total of 100 parts by weight of the compound having three or more acid anhydride groups, and a reaction solvent of 100 parts by weight or more is used. When a monohydroxy compound is further used as the necessary raw material compound, it is preferably a compound based on tetracarboxylic dianhydride, diamine, polyhydroxy compound, cationically polymerizable cyclic ether compound having a polymerizable group, and monohydroxy compound. The total amount is 100 parts by weight, and 100 parts by weight or more of the reaction solvent is used. When a compound having three or more acid anhydride groups and a monohydroxy compound are further used as the necessary raw material compound, it is preferably cationic polymerizable with respect to tetracarboxylic dianhydride, diamine, polyhydroxy compound, and polymerizable group. The total amount of the cyclic ether compound, the compound having three or more acid anhydride groups, and the monohydroxy compound was 100 parts by weight, and 100 parts by weight or more of the reaction solvent was used.

The polyester sulfamic acid (A) synthesized by using tetracarboxylic dianhydride, diamine, polyhydroxy compound, and cationically polymerizable cyclic ether compound having a polymerizable double bond includes raw materials of formula (4). The structural unit represented by the formula and the structural unit represented by the formula (5), each of which contains a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether having a polymerizable double bond derived from the starting material. An acid anhydride group, an amine group, a hydroxyl group, a polymerizable double bond or a monovalent organic group of a compound, or an additive other than these compounds. By including such a structure, hardenability becomes favorable.

The polyester amido acid (A) synthesized by using tetracarboxylic dianhydride, diamine, polyhydroxy compound, cationically polymerizable cyclic ether compound having a polymerizable double bond, and monohydroxy compound as raw materials includes the formula The structural unit represented by (4), the structural unit represented by formula (5) and the structural unit represented by formula (6), and the terminal thereof includes the acid anhydride group, amine group, hydroxyl group, polymerizable double bond, monovalent Organic groups, monovalent groups derived from monohydroxy compounds, or additives other than these compounds. By including such a structure, hardenability is improved, and as described above, the storage stability of the photosensitive composition is improved.

Polyesteramine (A) synthesized by using tetracarboxylic dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond as raw materials. ) Includes the structural unit represented by the formula (4) and the structural unit represented by the formula (5), and the terminal contains the acid anhydride group, a monovalent group derived from a compound having three or more acid anhydride groups, and an amine Groups, hydroxyl groups, polymerizable double bonds or monovalent organic groups or additives other than these compounds. By including such a structure, the transparency of a cured film improves as mentioned above.

Polyester synthesized by using a tetracarboxylic dianhydride, a compound having three or more acid anhydride groups, a diamine, a polyhydroxy compound, a cationic polymerizable cyclic ether compound having a polymerizable double bond, and a monohydroxy compound as raw materials. Amino acid (A) contains the structural unit represented by said Formula (4), the structural unit represented by Formula (5), and the structural unit represented by Formula (6), and the terminal contains the said acid anhydride group, and is derived from having A monovalent group, an amine group, a hydroxyl group, a polymerizable double bond, or a monovalent organic group of three or more acid anhydride group compounds, or an additive other than these compounds. By including such a structure, as mentioned above, transparency of a cured film improves, and the storage stability of a photosensitive composition improves.

The weight average molecular weight of the obtained polyester amidine (A) is preferably 1,000 to 200,000, and more preferably 3,000 to 50,000. If it exists in the said range, flatness and heat resistance will be favorable.

The weight average molecular weight in the present specification is a polystyrene-equivalent value obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml / min). Standard polystyrene can use polystyrene with a molecular weight of 645 ~ 132,900 (such as the Agilent Technologies polystyrene calibration kit PL2010-0102), and the column can use PLgel MIXED- D (Agilent Technology Co., Ltd.). Tetrahydrofuran (THF) can be used as the mobile phase. The weight average molecular weight of a commercially available product in this specification is a catalog value.

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

2-1. Polyesteramidic acid (A) having a polymerizable double bond The polyesteramidic acid (A) having a polymerizable double bond used in the photosensitive composition is the polyesteramidic acid (A).

2-2. Compound (B) having a polymerizable double bond 2-2-1. Compound having two or more polymerizable double bonds per molecule A polymerizable double bond used in the photosensitive composition described above The compound (B) is a compound having a polymerizable double bond other than the polyester amidate (A). The compound (B) having a polymerizable double bond is not particularly limited, except that it is not a polyester amidate (A), and is preferably a compound having two or more polymerizable double bonds per molecule.

When the compound (B) having a polymerizable double bond is 50 parts by weight to 300 parts by weight based on 100 parts by weight of the polyester amidic acid (A), the residual film rate after development becomes good.

Examples of the compound having two or more polymerizable double bonds in each molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di ( (Meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate, epichlorohydrin Diethylene glycol di (meth) acrylate, epichlorohydrin modified triethylene glycol di (meth) acrylate, epichlorohydrin modified tetraethylene glycol di (meth) acrylate, epichlorohydrin Modified polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) acrylate, epichlorohydrin modified dipropylene glycol di (meth) acrylate, epichlorohydrin modified tripropylene glycol di (Meth) acrylate, epichlorohydrin modified tetrapropylene glycol di (meth) acrylate, epichlorohydrin modified polypropylene glycol di (meth) acrylate, trimethylolpropane Alkane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, epichlorohydrin modified Trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, triglyceride Acrylate), epichlorohydrin modified glycerol tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (methyl) ) Acrylate, methoxylated cyclohexyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, and caprolactone Hydroxy valproic acid neopentyl glycol di (meth) acrylate, diglycerol tetra (meth) acrylate, diglycerol 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, Di-pentaerythritol tetra (meth) acrylate, di-pentaerythritol tri (meth) acrylate, di-pentaerythritol hexa (meth) acrylate, di-pentaerythritol hexa (meth) acrylate Esters, polyacid-modified (meth) acrylic oligomers, allyl cyclohexyl di (meth) acrylate, bis [(meth) acryloxy neopentyl glycol] adipate, bis Phenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, ethylene oxide modified bisphenol F bis (methyl) Base) acrylate, bisphenol S di (meth) acrylate, ethylene oxide modified bisphenol S di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 3-butanediol (meth) acrylate, dicyclopentyl diacrylate, polyester diacrylate, polyester triacrylate, polyester tetraacrylate, polyester pentaacrylate, polyester hexaacrylate, Ethylene oxide modified phosphate di (meth) acrylate, ethylene oxide modified phosphate tri (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, ethylene oxide modified Sex phosphate (Meth) acrylate, epichlorohydrin modified phthalic acid di (meth) acrylate, tetrabromobisphenol A di (meth) acrylate, triglycerol di (meth) acrylate, neoglutaric acid Alcohol modified trimethylolpropane di (meth) acrylate, isocyanurate ethylene oxide modified diacrylate, isocyanurate ethylene oxide modified triacrylate, caprolactone modified three [(Meth) acryloxyethyl] isocyanurate, (meth) acrylated isocyanurate, phenyl glycidyl ether acrylate / hexamethylene diisocyanate / carbamic acid Ester prepolymer, phenyl glycidyl ether acrylate / toluene diisocyanate / urethane prepolymer, pentaerythritol triacrylate / hexamethylene diisocyanate / urethane prepolymer, pentaerythritol triacrylic acid Ester / toluene diisocyanate / urethane prepolymer, pentaerythritol triacrylate / isophorone diisocyanate / urethane prepolymer, dipentaerythritol pentaacrylate / hexamethylene diisocyanate / amine Urethane prepolymer, non-yellowing type urethane acrylate, phenol novolac epoxy resin (Meth) acrylic acid modified products of fats, (meth) acrylic acid modified products of cresol novolac epoxy resins, carboxylic acid-containing urethane acrylate oligomers, and the like.

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

From the viewpoint of heat resistance and chemical resistance of the cured film, trimethylolpropane triacrylate, pentaerythritol triacrylate, and pentaerythritol tetra are preferred among compounds having two or more polymerizable double bonds per molecule. Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid modified (meth) acrylic acid oligomer, isocyanurate ethylene oxide modified diacrylate, isocyanurate ethylene oxide Modified triacrylate or a mixture of these.

As trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyacid modified (meth) acrylic acid oligomer, isocyanuric acid ring As the oxyethane-modified diacrylate, isocyanurate-ethylene oxide-modified triacrylate, or a mixture of these, the following commercially available products can be used.

A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name; East Asia Synthesis Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronix M-306 (65% to 70% by weight), M-305 (55% to 63% by weight), M-303 (30% to 60% by weight), M-452 (25% to 40% by weight), and M-450 (less than 10% by weight) (all are trade names; East Asia Synthetic Co., Ltd., the content rate in parentheses Table of contents of pentaerythritol triacrylate content in the mixture). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% to 60% by weight), M-400 (40% to 50% by weight), M -402 (30% to 40% by weight, hereinafter sometimes referred to as "M-402"), M-404 (30% to 40% by weight), M-406 (25% to 35% by weight), and M -405 (10% to 20% by weight) (both are trade names; East Asia Synthesis Co., Ltd., the content in parentheses is the listed value of the content of dipentaerythritol pentaacrylate in the mixture). Specific examples of the polyacid-modified (meth) acrylic acid oligomer are Aronix M-510 and Aronix M-520 (both trade names; East Asia Synthesis Co., Ltd.). A specific example of the isocyanuric acid ethylene oxide modified diacrylate is Aronix M-215 (trade name; East Asia Synthesis Co., Ltd.). A specific example of a mixture of isocyanuric acid ethylene oxide modified diacrylate and isocyanuric acid ethylene oxide modified triacrylate is Aronix M-313 (30% to 40% by weight). ) And Aronix M-315 (3% to 13% by weight) (both trade names; East Asia Synthesis Co., Ltd., the content in parentheses is the isocyanurate ethylene oxide in the mixture. Table of published values of the content ratios of sexual diacrylates). A specific example of the acrylic modified product of the phenol novolac epoxy resin is TEA-100 (trade name; KSM Co., Ltd.). A specific example of the acrylic modified product of a cresol novolac epoxy resin is CNEA-100 (trade name; KSM Co., Ltd.).

2-2-2. Compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule

From the viewpoint of resolvability, 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. If a compound having one polymerizable double bond in each molecule and at least one functional group selected from -OH and -COOH in each molecule is 1 part by weight based on 100 parts by weight of polyester amidate (A) ~ 50 parts by weight, the resolvability becomes good.

Examples of such a compound having one polymerizable double bond in each molecule and at least one functional group -OH and -COOH in each molecule include (meth) acrylic acid and hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) propenyloxy succinate Ethyl ester, 2- (meth) acrylfluorenyloxyethyl hexahydrophthalate, 2- (meth) acrylfluorenyloxyethyl phthalate, phthalic acid-2 -(Meth) acryloxyethyl-2-hydroxyethyl, 4-hydroxyphenyl (meth) acrylate, aniline p- (meth) acrylate, 4-hydroxybutyl (meth) acrylate , 1,4-cyclohexanedimethanol mono (meth) acrylate, hydroxyethyl (meth) acrylate, glycerol mono (meth) acrylate, 3- (2-hydroxyphenyl) acrylate, and ( (Meth) acrylic acid-β-carboxyethyl.

Among these compounds, 4-hydroxyphenyl (meth) acrylate and aniline p-hydroxy (meth) acrylate improve resolution.

2-3. Photopolymerization initiator (C) As long as the photopolymerization initiator contained in the photosensitive composition can contain polyester amidate (A), a compound (B) having a polymerizable double bond, and photo The composition of the polymerization initiator (C), the epoxy compound (D), and the additive (E) is not particularly limited as long as the polymerization starts.

Examples of the photopolymerization initiator contained in the photosensitive composition include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and xanthone , Thiaxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2- Hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2 , 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-ketone (for example, trade name: IRGACURE 907; BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1- (4-morpholinobenzene ) -Butanone-1 (for example, trade name: IRGACURE 369; BASF Japan Co., Ltd.), ethyl 4-dimethylaminobenzoate, 4-dimethylamine Isoamyl benzoate, 4,4'-bis (third butylperoxycarbonyl) benzophenone, 3,4,4'-tri (third butylperoxycarbonyl) benzoyl 1,1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzylideneoxime) (eg, trade name: IRGACURE) OXE01, BASF, Japan (BASF Japan Co., Ltd.), ethyl ketone, 1- [9H-ethyl-6- (2-methylbenzylidene) -9-carbazol-3-yl]-, 1- (O-ethyl Fluorenyl oxime) (for example, trade name: IRGACURE OXE02, BASF Japan Co., Ltd.), IRGACURE OXE03 (trade name; BASF Japan Co., Ltd.) , 1,2-propanedione-1- [4-[[4- (2-hydroxyethoxy) phenyl-] thio] phenyl] -2- (O-acetamidoxime) (for example, commercial products Name: Adeka arc Luz NCI-930, ADEKA Co., Ltd.), Adeka arc Luz NCI-831 (trade name; Adeco ( ADEKA) Co., Ltd.), Adeka Optomer N-1919 (trade name; ADEKA Co., Ltd.), 2,4,6-trimethylbenzyl Phenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -triazine, 2- (3 ', 4'-dimethoxybenzene Alkenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl)- Mesazine, 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -mesatriazine, 2- (4'-pentoxystyryl) -4, 6-bis (trichloromethyl) -mesytriazine, 4- [p-N, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -mesytriazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) ) -Triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3, 3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2-methyl-2-morpholino (Propanyl) -9 -N-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone and bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H- Pyrrol-1-yl) -phenyl) titanium and the like.

The photopolymerization initiator may be used alone or in combination of two or more. Among the photopolymerization initiators, from the viewpoints of the sensitivity of the coating film at the time of exposure and the transparency of the cured film, α-aminobenzoyl ketone, fluorenyl phosphine oxide, and oxime ester photopolymerization initiators are preferred. In this specification, a thin film obtained by pre-drying (pre-baking) a thin film of a photosensitive composition formed on a substrate by spin coating, printing, or other methods is referred to as a "coating film". After the coating film is subjected to subsequent steps of exposure, development, cleaning, and drying, it is formally cured (post-baking) to form a hardened film. In this specification, the films in the steps from the pre-drying to the drying are referred to as "coating films", and are expressed by expressions such as "coating film upon exposure", "coating film after development", and the like. Which step of the film step is the coating film.

From the viewpoint of the sensitivity of the coating film and the transparency of the cured film, among the photopolymerization initiators, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- is more preferred. (O-benzylidene oxime) or 1,2-propanedione-1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl] -2- (O-ethyl Fluorenyl oxime) is 20% by weight or more based on the total weight of the photopolymerization initiator. Moreover, if it is 50 weight% or more, it is more preferable. The photopolymerization initiator may also contain only 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzylideneoxime) or 1,2-propanedione- 1- [4-[[4- (2-hydroxyethoxy) phenyl] thio] phenyl] -2- (O-acetamidooxime).

2-4. 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 an epoxy compound (D) to the photosensitive composition of this invention, the heat resistance of a cured film can be improved. When the epoxy compound (D) is 20 parts by weight to 150 parts by weight based on 100 parts by weight of the polyester amidate (A), the flatness becomes good.

As a preferred example of the epoxy compound, 3,4-epoxycyclohexanecarboxylic acid-3 ', 4'-epoxycyclohexyl methyl ester (for example, trade name: Celloxide 2021P, Daicel Co., Ltd.), 1-methyl-4- (2-methyloxetanyl) -7-oxabicyclo [4.1.0] heptane (for example, trade name: Xeroxes Celloxide 3000, Daicel Co., Ltd.), 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4- ([2,3-glycidoxy] phenyl)] ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-glycidoxy) benzene Yl] -1- [4- [1- [4- (2,3-glycidoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propyl A mixture of alcohols, 2- [4- (2,3-glycidoxy) phenyl] -2- [4- [1,1-bis [4-([2,3-glycidoxy)] Phenyl)] ethyl] phenyl] propane (for example, trade name: TECHMORE VG3101L, Printec Co., Ltd.), 1,1,1-tris (4-hydroxyphenyl) ethyl Triglycidyl ether (for example, trade name: jER 1032H60, Mitsubishi Chemical Corporation), 1,3-bis (oxetanylmethyl) -5- (2-propenyl) -1 , 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2-bis (hydroxymethyl) -1-butanol's 1,2-epoxy-4- (2-oxetanyl) cyclohexane adduct (for example, trade name: EHPE-3150, Daicel Co., Ltd.), jER YX4000, YX4000H, YL6121H (all trade names; Mitsubishi Chemical Corporation) Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3100 (all are trade names; Nippon Kayaku Co., Ltd.) and so on.

2-5. The ratio of the polyester amidate (A), the compound (B) having a polymerizable double bond, the photopolymerization initiator (C), and the epoxy compound (D) is relatively high in the photosensitive composition. The ratio of the compound (B) having a polymerizable double bond to 100 parts by weight of the polyester amidine (A) is 20 to 300 parts by weight. When the ratio of the compound (B) having a polymerizable double bond is within the above range, the balance between heat resistance, flatness, chemical resistance, and residual film rate after development is good. The compound (B) having a polymerizable double bond is more preferably in the range of 100 parts by weight to 300 parts by weight.

In the photosensitive composition, the ratio of the epoxy compound (D) to 20 parts by weight to 200 parts by weight based on 100 parts by weight of the polyester amidate (A). When the ratio of the epoxy compound (D) is within the above range, the balance between heat resistance and flatness is good. If the ratio of an epoxy compound (D) exists in the range of 20 weight part-150 weight part, it is more preferable.

2-6. Additives (E) Various additives can be added to the photosensitive composition to improve coating uniformity, adhesion, transparency, resolution, flatness, and chemical resistance. Examples of additives include anionic, cationic, nonionic, fluorine or silicon based leveling agents / surfactants, coupling agents such as silane coupling agents, hindered phenol, hindered amine, phosphorus, and sulfur compounds Such as antioxidants, molecular weight regulators, epoxy hardeners.

2-6-1. Surfactant A surfactant may be added to the photosensitive composition to improve coating uniformity. Specific examples of the surfactant include Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, and Polyflow No. 90. Polyflow No. 95 (both trade names; Gongrongshe Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Dispar Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Dispar Disperbyk 181, Disperbyk 182, BYK-300, BYK-306, BYK-310, BYK-320, Bi BYK-330, BYK-342, BYK-346, BYK-361N, BYK-UV3500, BYK-UV3570 (all products) Name; BYK Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all are trade names; Shin-Etsu Chemical Industry Co., Ltd. Division), Surflon SC-101, Surflon KH-40, Surflon S611 (both trade names; AGC Seimi Chemical Co., Ltd.), Fuji Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Fudge (Ftergent) 602A, Ftergent 650A, FTX-218 (both trade names; Neos Co., Ltd.), Eftop (EFTOP) EF-351, Eftop (EFTOP) EF- 352, Eftop (EFTOP) EF-601, Eftop (EFTOP) EF-801, Eftop (EFTOP) EF-802 (the above are all trade names; Mitsubishi Material Co., Ltd.), Mega (Megafac) F-171, Megafac (F-177), Megafac (F-410), Megafac (F-430), Megafac (F-444), Megafac (F) -472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac F-559, Megafac R-30, Megafac R-94, Megafac RS-75, Megafac RS-72-K , Megafac RS-76-NS, Megafac DS-21 (both trade names; DIC Corporation), TEGO Twin 4000, TEGO Twin Twin) 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, Tegola TEGO Rad 2200N, TEGO Rad 2250N (both trade names, Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzene sulfonate, fluoroalkyl Carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetra (fluoroalkyl polyoxyethylene ether), fluoroalkyl Methyl ammonium salt, fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oil Alkenyl 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 Lauric acid ester, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate and alkane Diphenyl ether disulfonate. It is preferable to use at least one selected from these surfactants.

Among these surfactants, if selected from the group consisting of BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, and safuron ( Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac (Megafac) F-556, Megafac F-559, Megafac RS-72-k, Megafac DS-21, TEGO Twin 4000, Fluoroalkylbenzenesulfonate Salt, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amino sulfonate It is preferable that the coating uniformity of the composition is high.

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

2-6-2. Coupling agent From the viewpoint of further improving the adhesion between the formed cured film and the substrate, the photosensitive composition of the present invention may further contain a coupling agent.

As such a coupling agent, for example, a silane-based, aluminum-based, or titanate-based coupling agent can be used. Specific examples include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy Silane (for example, trade name: Sila-Ace S510, JNC Corporation), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name Name: Sila-Ace S530, JNC Co., Ltd., 3-Mercaptopropyltrimethoxysilane (for example, trade name: Sila-Ace S810, Czech Republic Co., Ltd. (JNC) Co., Ltd., a copolymer of 3-glycidyloxypropyltrimethoxysilane (for example, trade name: CoatOSil MP200, Momentive Performance Materials Co., Ltd. ) And other silane-based coupling agents, aluminum coupling agents such as aluminum acetoxy aluminum diisopropoxide, and titanate-based coupling agents such as tetraisopropylbis (dioctyl phosphite) titanate.

Among these coupling agents, 3-glycidoxypropyltrimethoxysilane is preferable because it has a large effect of improving the adhesiveness.

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

2-6-3. Antioxidant From the viewpoint of improving transparency and preventing yellowing when the cured film is exposed to high temperatures, the photosensitive composition may further contain an antioxidant.

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 these, from the viewpoint of weather resistance, a hindered phenol type is preferred. Specific examples include: Irganox 1010, Irganox 1010FF, Irganox 1035, Irganox 1035FF, and Yilu Jia Irganox 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Yilujia Irganox 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Yilu Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yilu Irganox 565DD, Irganox 295 (both trade names; BASF Japan), ADK STAB AO-20, Adikos ADK STAB AO-30, ADK STAB AO-50, ADK STAB ) AO-60, ADK STAB AO-70, ADK STAB AO-80 (both trade names; ADEKA Co., Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferred.

An 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 adjuster The photosensitive composition may further contain a molecular weight adjuster to suppress an increase in molecular weight due to polymerization and exhibit excellent resolution. Examples of the molecular weight modifier include thiols, xanthonic acids, 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, and 2,5-di-third-butyl Hydroquinone, hydroquinone, methylhydroquinone, third butylhydroquinone, methoquinone, p-benzoquinone, methyl-p-benzoquinone, third butyl-p-benzoquinone, anthraquinone, n-hexylsulfide Alcohol, n-octyl mercaptan, n-dodecyl mercaptan, tertiary-dodecyl mercaptan, thioglycolic acid, dimethyl xanthate sulfide, diisopropyl xanthate disulfide, 2 , 4-diphenyl-4-methyl-1-pentene and the like.

The molecular weight modifiers may be used alone or in combination of two or more. Among the molecular weight modifiers, a naphthoquinone-based molecular weight modifier is preferred in terms of exhibiting excellent resolution.

Among molecular weight modifiers, 2-hydroxy-1,4-naphthoquinone having a phenolic hydroxyl group is more preferred from the viewpoint of resolvability. From the viewpoint of resolvability, it is preferable to include the molecular weight modifier such that the content of the photopolymerization initiator (C) is more than 5.0 times and less than 30 times the content of the molecular weight modifier, and more preferably the photopolymerization initiator is used. The molecular weight modifier is contained so that the content of the agent (C) is 5.1 times and 20 times the content of the molecular weight modifier. It is more preferable that the molecular weight modifier is contained so that the content of the photopolymerization initiator (C) is 5.2 times to 10 times the content of the molecular weight modifier.

2-6-5. Epoxy hardener The photosensitive composition may further contain an epoxy hardener to improve flatness and chemical resistance. As the epoxy hardener, there are thermosensitive properties such as an acid anhydride hardener, an amine hardener, a phenol hardener, an imidazole hardener, a catalyst hardener, and a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a sulfonium salt. From the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film, the acid generator and the like are preferably an acid anhydride-based hardener or an imidazole-based hardener.

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 hexahydrophthalic anhydride. Hydrogen trimellitic anhydride and the like, aromatic polycarboxylic anhydrides such as phthalic anhydride and trimellitic anhydride. Among these acid anhydride-based hardeners, trimellitic anhydride and hexahydrotrimellitic anhydride which can improve the heat resistance of the cured film without impairing the solubility of the photosensitive composition in the solvent are preferred.

Specific examples of the imidazole-based hardener include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-diimidazole. Hydrogen-1H-pyrrolo [1,2-a] benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these imidazole-based hardeners, 2-undecylimidazole which can improve the hardenability of the cured film without impairing the solubility of the photosensitive composition in a solvent is particularly preferred.

The ratio of the epoxy curing agent to the epoxy compound (D) is 100 parts by weight relative to the epoxy compound (D), and the epoxy curing agent is 0.1 to 60 parts by weight. For example, in the case where the epoxy hardener is an acid anhydride-based hardener, in more detail, it is preferred that the carboxylic anhydride group or carboxyl group in the epoxy hardener is 0.1 times equivalent to the epoxy group. Add ~ 1.5 times equivalent. At this time, the carboxylic acid anhydride group is calculated at a divalent value. When a carboxylic acid anhydride group or a carboxyl group is added so that it may become 0.15-times equivalent to 0.8-times equivalent, chemical resistance is further improved, and it is further more preferable.

2-6-6. Ultraviolet absorbent The photosensitive composition may further include an ultraviolet absorbent from the viewpoint of further improving the deterioration suppressing ability of the patterned transparent film to be formed.

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

0.01 to 10 parts by weight of an ultraviolet absorber is added to the total amount of the photosensitive composition and used.

2-6-7. Anti-agglomerating agent The photosensitive composition may further include an anti-agglomerating agent from the viewpoint of preventing a solid component from being fused with a solvent and preventing aggregation.

Specific examples of the anti-coagulant are Disperbyk-145, Disperbyk-161, Disperbyk-162, Disperbyk-163 , Disperbyk-164, Disperbyk-182, Disperbyk-184, Disperbyk-185, Disperbyk (Disperbyk) -2163, Disperbyk-2164, BYK-220S, Disperbyk-191, Disperbyk-199, Dispar Disperbyk-2015 (both trade names; BYK Chemie Japan Co., Ltd.), FTX-218, Ftergent 710FM, Ftergent 710FS (all trade names, Neos Co., Ltd.), Flowlen G-600, Flowlen G-700 (all are trade names, Kyoeisha Chemical Co., Ltd.).

0.01 to 10 parts by weight of an anti-agglomerating agent is added to the total amount of the photosensitive composition and used.

2-6-8. From the viewpoint of further improving heat resistance, chemical resistance, in-plane uniformity, flexibility, flexibility, and elasticity, the photosensitive composition may further include thermal crosslinking联 剂。 Union agent.

Specific examples of the thermal crosslinking agent are Nikalac MW-30HM, Nikalac MW-100LM, Nikalac MW-270, Nikalac MW-280, Nikalac Nikalac MW-290, Nikalac MW-390, Nikalac MW-750LM (both trade names; Sanwa Chemical (stock)).

A thermal 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 From the viewpoint of improving the resolution, the photosensitive composition may further include a photoacid generator. As the photoacid generator, a 1,2-quinonediazide compound can be used. Specific examples of 1,2-quinonediazide compounds are: 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4-triazine Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate , 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-4-sulfonate, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3, 3 ', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3', 4-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4 ' -Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate Acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate; bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide 4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate; tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide -4-sulfonate, Tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1,1-tris (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide 4-sulfonate, 1,1,1-tris (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonate; bis (2,3,4-trihydroxybenzene Methane) -1,2-naphthoquinonediazide-4-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate , 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonate, 2,2-bis (2,3,4-trihydroxy Phenyl) propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane- 1,2-naphthoquinonediazide-4-sulfonate, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthalene Quinonediazide-5-sulfonate; 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol- 1,2-naphthoquinonediazide-4-sulfonate, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene Propyl] bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthalene Quinonediazide-4-sulfonate, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Alkane-1,2-naphthoquinonediazide-5-sulfonate; 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3', 3'-tetramethyl-1,1'-spirobiindene-5, 6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonate; 2,2,4-trimethyl-7,2 ', 4'- Trihydroxyflavan (flavane) -1,2-naphthoquinonediazide-4-sulfonate and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2 -Naphthoquinonediazide-5-sulfonate. 0.01 to 10 parts by weight of a photoacid generator is added to the total amount of the photosensitive composition and used.

2-6-10. Other additives The photosensitive composition may further contain a polymer (hereinafter sometimes referred to as a “radical copolymer”) which is represented by the following formula (7) The radical polymerizable compound (P1), the radical polymerizable compound (P2) having an alkoxysilyl group, and the radical polymerizable compound (P3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group. Free radical copolymerization. In formula (7), R ⁶ is hydrogen or methyl, R ⁷ to R ¹⁰ are alkyl groups having 1 to 5 carbon atoms, R ¹¹ is alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n It is an integer from 1 to 150.

2-6-10-1. Radical polymerizable compound (P1) The radical polymerizable compound (P1) represented by the formula (7) functions as a surfactant. Therefore, by using (P1) in the raw material, By making the radical copolymer to function as a surfactant, even without adding a surfactant, the flatness, the adhesion to the base substrate, and the coatability can be improved. By adding a radical polymerizable compound (P1), a radical copolymer polymer becomes easy to surface on a film surface.

In the photosensitive composition, in the radical polymerizable compound (P1) represented by the formula (7), R ⁶ is preferably hydrogen or methyl, R ⁷ to R ¹⁰ are methyl, and R ¹¹ is carbon number. A compound having 1 to 10 alkyl groups, m being an integer of 1 to 5, and n being an integer of 1 to 150. More preferred are compounds in which 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. Further, n is an integer of 30 to 70. The compound is particularly preferably a compound in which n is an integer of 50 to 70. The weight-average molecular weight of the radical polymerizable compound (P1) represented by the formula (7) is preferably 500 to 8000.

The radically polymerizable compound (P1) can be produced by a known method. Alternatively, a commercially available product may be used. Examples include FM-0711, FM-0721, and FM-0725 (both are trade names; JNC Corporation).

2-6-10-2. Radical polymerizable compound (P2) having alkoxysilyl group In the photosensitive composition, a radical polymerizable compound (P2) having alkoxysilyl group is used A raw material for the free radical copolymer is obtained. A preferred radical polymerizable compound (P2) is selected from the group consisting of 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (Meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxy One or more of the group consisting of a silylsilane and a p-styryltrimethoxysilane. Among these radically polymerizable compounds, 3- (meth) propenyloxypropyltrimethoxysilane and 3- (meth) propenyloxypropyltriethoxysilane have good flatness and are preferred. By using (P2), transparency, chemical resistance, etc. are improved. In addition, the silane coupling effect improves the adhesion to the substrate.

2-6-10-3. Radical polymerizable compound (P3) having at least one of epoxy group, carboxyl group, and hydroxyphenyl group The photosensitive composition will have epoxy group, carboxyl group, and hydroxyphenyl group At least one of the radical polymerizable compounds (P3) is used as a raw material to obtain the radical copolymer polymer. A preferable radical polymerizable compound (P3) is selected from glycidyl (meth) acrylate, glycidyl 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, and 4-hydroxyphenylvinyl. More than one of the group of ketones. (P3) functions as a cross-linking agent for polymers and contributes to the improvement of heat resistance and chemical resistance.

2-6-10-4. Method for producing radical copolymerization polymer The radical copolymerization polymer is obtained by radically polymerizing a radical polymerizable compound (P1) represented by formula (7) and an alkoxysilyl group. The radical compound (P2) and the radically polymerizable compound (P3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group are obtained by radical copolymerization. The method for producing a radical copolymer is not particularly limited, and the radical polymerizable compound can be heated in the presence of a radical initiator to produce a radical copolymer. As the radical initiator, an organic peroxide, an azo compound, or the like can be used. The reaction temperature for radical copolymerization is not particularly limited, but is usually in the range of 50 ° C to 150 ° C. The reaction time is not particularly limited, but is usually in the range of 1 hour to 48 hours. In addition, the reaction can be performed under any pressure of increased pressure, reduced pressure, or atmospheric pressure.

It is preferable that the solvent used for the said radical copolymerization reaction is a solvent which melt | dissolves the produced | generated polymer. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, and ethyl methoxyacetate. Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate Ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy 4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethyl Ester, 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. The solvent may be one of these specific examples or a mixture of two or more of these specific examples.

Regarding the radical copolymer polymer used in the photosensitive composition, a solvent used in the polymerization can be left directly to make a radical copolymer polymer solution in consideration of workability and the like, and the solvent can be removed. In addition, it is made into a solid radical copolymer in consideration of handling properties.

When the radical copolymerized polymer has a weight average molecular weight in the range of 1,000 to 50,000 obtained by GPC analysis using polystyrene as a standard, the film-forming property is good, which is preferable. Furthermore, if the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the cured film is good and more preferable. Furthermore, if 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 good, which is particularly preferable.

Based on the total amount of the photosensitive composition, 0.1 to 20 parts by weight of other additives are added and used.

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 preferably a soluble polyester amidate (A), a compound (B) having a polymerizable double bond, a photopolymerization initiator (C), and an epoxy compound (D ) And other solvents. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, and ethyl acetate. Methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl 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, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy- Methyl 2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate Ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy 4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethyl Ester, 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. The solvent may be one of these specific examples or a mixture of two or more of these specific examples.

2-8. Storage of Photosensitive Composition When the photosensitive composition is stored in a range of -30 ° C to 25 ° C, the stability of the composition over time is improved. When the storage temperature is -20 ° C to 10 ° C, it is more preferable because there is no precipitate.

3. The cured film of the photosensitive composition The photosensitive composition can be obtained by polyester polyester amine acid (A), a compound having a polymerizable double bond (B), and a photopolymerization initiator (C). The epoxy compound (D) and the additive (E) are mixed, and a solvent is optionally added as needed, and these compounds are mixed and dissolved uniformly. As the additive (E), a coupling agent, a surfactant, and other additives can be selected and used as required according to the target characteristics.

A coating film can be formed by applying the photosensitive composition prepared as described above (in a solid state without a solvent, after dissolving in a solvent) to the surface of a substrate and removing the solvent by, for example, heating. A conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexographic printing method, a spray method, or a slit coating method can be used for coating the photosensitive composition on the substrate surface. Next, the coating film is heated (pre-baked) using a hot plate, an oven, or the like. The heating conditions vary depending on the type of each component and the blending ratio, and are usually 70 ° C to 150 ° C, 5 minutes to 15 minutes in an oven, and 1 minute to 5 minutes in a heating plate.

Thereafter, the coating film was irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet irradiation is preferably 5 mJ / cm ² to 1000 mJ / cm ² in an i-ray meter. The photosensitive composition irradiated with ultraviolet rays becomes a three-dimensional crosslinked body by polymerization of a compound having a polymerizable double bond, and is insoluble in an alkaline developing solution.

Next, the coating film is immersed in an alkaline developing solution by spray development, spray development, coating development, immersion development, or the like, and unnecessary portions are dissolved and removed. Specific examples of the alkaline developer are aqueous solutions of inorganic bases such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic bases such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. In addition, an appropriate amount of methanol, ethanol, a surfactant, and the like may be added to the alkaline developing solution and used.

Finally, in order to completely harden the coating film, a hardened film can be obtained by heat treatment, which is performed at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and in an oven, for 30 minutes to 90 minutes, In the case of a hot plate, it is performed for 5 to 30 minutes.

When the cured film obtained as described above is heated, further 1) the polyamidic acid of the polyester amidate (A) is partially dehydrated and cyclized to form an amidine bond, and 2) the carboxylic acid of the polyester amidate It reacts with an epoxy-containing polymer and has a high molecular weight, so it is very tough, and has excellent transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a color filter can be used to produce a liquid crystal display element or a solid-state imaging element. In addition to the protective film for color filters, if the cured film of the present invention is used as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode, or formed between a transparent electrode and an alignment film A transparent insulating film is also effective. Furthermore, the cured film of the present invention is also effective as a protective film for a light emitting diode (Light Emitting Diode, LED) light emitting body. [Example]

Next, the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples. [Synthesis Example 1] Synthesis of polyester amido acid (A1) having a polymerizable double bond

In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (PGMEA), 1,2,3,4-butane tetrahydrate, which had been dehydrated and purified, were charged in the following order by weight. Carboxylic dianhydride (BT-100), SMA1000P (trade name; styrene-maleic anhydride copolymer, Sichuan Crude Chemical Co., Ltd.), benzyl alcohol, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), Stir for 6 hours at 125 ° C under a dry nitrogen stream (first step of synthesis). PGMEA 43.10 g BT-100 2.52 g SMA1000P 12.01 g benzyl alcohol 3.67 g 4HBAGE 4.24 g

Thereafter, the solution after the reaction was cooled to 25 ° C., 3,3′-diaminodiphenylphosphonium (DDS) and PGMEA were added at the following weights, and the mixture was stirred at 20 ° C. to 30 ° C. for 2 hours, and then at 125 ° C. Stir for 1 hour at 2 ° C (second step in synthesis). DDS 0.79 g 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% by weight solution (A1) of a pale yellow transparent polyester amidine. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A1) was 32,300.

[Synthesis Example 2 to Synthesis Example 7] Synthesis of polyester lysine solution (A2 to A7) According to the method of Example 1, each component was reacted under the weight (unit: g), temperature, and time described in Table 1. To obtain a polyester amidine solution. In addition, regarding the names in Table 1, PGMEA represents propylene glycol monomethyl ether acetate, ODPA represents 4,4'-diphenyl ether tetracarboxylic dianhydride, GMA represents glycidyl methacrylate, and Oxe-30 represents ( 3-ethyloxetane-3-yl) methyl methacrylate.

Table 1

[Synthesis Example 8] Synthesis of polyester amidine (A8) having a polymerizable double bond In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate subjected to dehydration purification was sequentially loaded at the following weight. (PGMEA), 1,2,3,4-butanetetracarboxylic dianhydride (BT-100), SMA1000P (trade name; styrene-maleic anhydride copolymer, Sichuan Crude Chemical Co., Ltd.), benzyl alcohol Under stirring in a stream of dry nitrogen at 125 ° C for 2 hours (the first step of the synthesis). PGMEA 26.74 g BT-100 1.91 g SMA1000P 9.12 g benzyl alcohol 2.79 g

Thereafter, the solution after the reaction was cooled to 25 ° C., 3,3′-diaminodiphenylphosphonium (DDS) and PGMEA were added at the following weights, and the mixture was stirred at 20 ° C. to 30 ° C. for 2 hours, and then at 125 ° C. Stir for 1 hour at 2 ° C (second step in synthesis). DDS 0.60 g PGMEA 4.41 g

Thereafter, the solution after the reaction was cooled to 25 ° C, and glycidyl methacrylate (GMA), 1-methylimidazole (NMI), and 4-methoxyphenol (MQ) were charged at the following weights, and the temperature was at 80 ° C. Stir for 8 hours (third step of synthesis). 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% by weight solution of light yellow transparent polyester amidate ( A8). A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A8) was 14,700.

[Synthesis Example 9 to Synthesis Example 11] Synthesis of polyester lysine solution (A9 to A11) According to the method of Example 8, each component was reacted under the weight (unit: g), temperature, and time described in Table 2. To obtain a polyester amidine solution.

Table 2

[Comparative Synthesis Example 1 and Comparative Synthesis Example 2] Synthesis of polyester lysine solution (a1 and a2) According to the method of Example 1, each of the weights (unit: g), temperature, and time described in Table 3 was used. The components are reacted to obtain a polyester amidine solution (a1) and a polyester amidine solution (a2).

table 3

[Comparative Synthesis Example 3] Synthesis of polyester amidine solution (a3) In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (PGMEA) subjected to dehydration purification was sequentially loaded at the following weight, 1,2,3,4-butanetetracarboxylic dianhydride (BT-100), SMA1000P (trade name; styrene-maleic anhydride copolymer, Sichuan Crude Chemical Co., Ltd.), benzyl alcohol, methacrylic acid Glycidyl ester (GMA) and 3,3'-diaminodiphenylphosphonium (DDS) were stirred under a stream of dry nitrogen at 125 ° C for 2 hours. PGMEA 49.85 g BT-100 2.66 g SMA1000P 12.66 g benzyl alcohol 3.87 g GMA 3.18 g DDS 0.83 g [Z / Y = 2.7, (Y + Z) /X=0.9, W / (2X + rV) = 0.25] produced White insoluble matter was obtained and a uniform solution could not be obtained.

[Comparative Synthesis Example 4] Synthesis of polyester sulfamic acid solution (a4) According to the method of Comparative Synthesis Example 3, each component was reacted under the weight (unit: g), temperature, and time described in Table 4, but it was not obtained A homogeneous solution of polyester amidine.

Table 4

[Example 1] A 500 ml separable flask with a stirring wing was subjected to nitrogen replacement, and the weight (unit: g) shown in Table 5-1 was charged into the flask and the weight obtained in Synthesis Example 1 was charged. Polyester Amino Acid Solution (A1) (Polyester Amino Acid (A) Component), U-6LPA (Shin Nakamura Chemical Industry Co., Ltd.) (Compound (B) Component Having Polymerizable Double Bond), NCI-930 (ADEKA Co., Ltd.) (photopolymerization initiator (C) component), VG3101L (epoxy compound (D) component), trimellitic anhydride (TMA), 3-glycidoxypropyltrimethoxysilane (For example, trade name: Sila-Ace S510, JNC Co., Ltd.), AO-60 (ADEKA Co., Ltd.), Quinoexter ) QE-3124 (Kawasaki Chemical Industry Co., Ltd.) (additive (E) component) and dehydrated and purified PGMEA and EDM. Stir at room temperature for 3 hours to uniformly dissolve. Next, BYK-342 (BYK Additives & Instruments) was put in, stirred at room temperature for 1 hour, and filtered with a membrane filter (0.2 μm) to prepare a photosensitive composition. .

[Example 2 to Example 11] According to the method of Example 1, each component was mixed with the weight (unit: g) described in Table 5-1 and Table 5-2 to obtain a photosensitive composition.

Table 5-1

In the table, "M-402" indicates a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; Aronix M-402 (East Asia Synthesis Co., Ltd.), and "RS-72-K" indicates surface activity Agent; Megafac RS-72-K (Di Edison (DIC) Co., Ltd.) (the same below).

Table 5-2

"M-520" in the table indicates a polyacid-modified (meth) acrylic oligomer; Aronix M-520 (East Asia Synthesis Co., Ltd.), and "EHPE3150" indicates 2,2-bis (hydroxy 1,2-epoxy-4- (2-oxetanyl) cyclohexane adduct of methyl) -1-butanol; EHPE3150 (Daicel Co., Ltd.), "F- "556" stands for surfactant; Megafac F-556 (DIC Corporation).

These photosensitive compositions were spin-coated on a glass substrate at 950 rpm for 10 seconds, and pre-baked on a hot plate at 100 ° C for 80 seconds. Next, a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) was used with an exposure gap of 100 μm through a mask having holes and line patterns with a width of 50 μm in the air. Make an exposure. The exposure amount was measured using a cumulative light meter UIT-102 (trade name; Ushio Electric Co., Ltd.) and a light receiver UVD-365PD (trade name; Ushio Electric Co., Ltd.) to set 30 mJ. / cm ² . After the exposed coating film was developed using a NaHCO ₃ aqueous solution at 27 ° C. for 40 seconds, the coating film was washed with running water (pure water) for 20 seconds. After further baking in an oven at 230 ° C. for 30 minutes, a glass substrate with a pattern-shaped cured film having a film thickness of 1.5 μm was obtained.

With respect to the cured film obtained as described above, the residual film rate and 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 rate after development] The step, surface roughness, and fine shape measuring device (trade name: P-16, KLA TENCOR Co., Ltd.) were used to measure the film thickness before and after development. And calculate the residual film rate after development (film thickness after development × 100 / film thickness before development). A case where the residual film rate after development was 80% or more was ◎, a case where the residual film rate after development was 75% or more was ○, and a case where the residual film rate after development was less than 75% was ×. Here, before development means "after pre-baking", and after development means "after washing and drying."

[Evaluation method of analytical property] The obtained glass substrate with a patterned transparent body was observed with a 1,000-times optical microscope, and the resolvability of the hole pattern of 20 μm was confirmed. The case where the analysis was performed was set to "○", and the case where the residue was left unanalyzed was set to "x".

Table 6-1

Table 6-2

[Comparative Example 1 to Comparative Example 4] According to the method of Example 1, each component was mixed and dissolved with the weight (unit: g) of Table 7 to obtain a photosensitive composition.

Table 7

Regarding the cured film obtained by the method of the example, the residual film rate and resolution after development were evaluated according to the example. The results are shown in Table 8.

Table 8

From the results shown in Table 6-1 and Table 6-2, it was found that the cured film of the photosensitive composition containing the polyester amidino acid (A) having a polymerizable double bond in Examples 1 to 11 was obtained. The balance between the residual film rate and the resolution after development was obtained. On the other hand, as shown in Table 8, the cured film using Comparative Examples 1 to 4 having a photosensitive composition containing a polyester amidino acid had a poor residual film rate after development.

As described above, by using the polyester amidine (A) having a polymerizable double bond, the residual film rate and resolution after development can be satisfied: the polyester amidine (A) having a polymerizable double bond is A reactant containing a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond as raw materials. [Industrial availability]

The cured film obtained from the photosensitive composition of the present invention has excellent properties as optical materials, such as heat resistance, transparency, flatness, resolution, and residual film rate. Therefore, it can be used as a color filter, an LED light-emitting element, and light. A protective film for a receiving element and the like, and also used as a transparent insulating film formed between a TFT and a transparent electrode or between a transparent electrode and an alignment film.

no

no

Claims (12)

A polyester amido acid (A), which is a reactant of a raw material comprising a tetracarboxylic dianhydride, a diamine, a polyhydroxy compound, and a cationically polymerizable cyclic ether compound having a polymerizable double bond, and in the raw material, The ratio of the following formula (1), formula (2), and formula (3) to be established includes X mol tetracarboxylic dianhydride, Y mol diamine, Z mol polyhydric hydroxy compound, and W Mol's cationically polymerizable cyclic ether compound having a polymerizable double bond, 0.2 ≦ Z / Y ≦ 8.0 ··········· (1) 0.2 ≦ (Y + Z) / X ≦ 5.0 ····· (2) 0.05≤W / 2X≤1.0 ·········· (3). The polyester amido acid (A) according to item 1 of the scope of patent application, which is a reactant of the raw material further containing a compound having three or more acid anhydride groups, and the raw material is such that the following formula (1) The ratios in which the relationships of formula (2) and formula (3 ′) are established include X mol tetracarboxylic dianhydride, Y mol diamine, Z mol polyhydric hydroxy compound, and W mol have Cationic polymerizable cyclic ether compound with polymerizable double bond and compound with three or more acid anhydride groups in V mole, 0.2 ≦ Z / Y ≦ 8.0 ············ (1) 0.2 ≦ (Y + Z) /X≦5.0 ····· (2) 0.05 ≦ W / (2X + rV) ≦ 1.0 ···· (3 ') The compound having three or more acid anhydride groups is Each molecule contains r acid anhydride groups and is used in an amount of 0.1 to 500 parts by weight with respect to 100 parts by weight of the total amount of tetracarboxylic dianhydride, diamine, and polyhydroxy compound. Compound. The polyester amidate (A) according to item 1 or 2 of the scope of the patent application, which comprises a structural unit represented by the following formula (4) and a structural unit represented by the formula (5), In the formula, 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 two -OH from a polyhydroxy compound, R ^{5 is} independently H or a group having a polymerizable double bond, and not all R ⁵ in the polyester amido acid (A) is H . The polyester amido acid (A) according to item 1 or item 2 of the patent application scope, wherein the raw material further contains a monohydroxy compound. The polyester amidamic acid (A) according to item 4 of the scope of patent application, which includes a structural unit represented by the following formula (4), a structural unit represented by the formula (5), and Building blocks, In the formula, 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 2 -OH from a polyhydroxy compound, R ⁴ is a residue obtained by removing -OH from a monohydroxy compound, R ^{5 is} independently H or a group having a polymerizable double bond, and Not all R ⁵ in the polyester amidine (A) is H. The polyester amido acid (A) according to claim 1, 2, or 4, wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond has (meth) acrylic acid Oxy and has glycidyl or oxetanyl. The polyester amido acid (A) according to claim 1, 2, or 4, wherein the cationically polymerizable cyclic ether compound having a polymerizable double bond is selected from glycidyl acrylate , Glycidyl methacrylate, 2-methyl glycidyl methacrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6, acrylic acid, 7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methyl 3,4-epoxycyclohexyl methyl acrylate, 3- (propenyloxymethyl) oxetane, 3- (propenyloxymethyl) -2-methyloxa Cyclobutane, 3- (propenyloxymethyl) -3-ethyloxetane, 3- (propenyloxymethyl) -2-phenyloxetane, 3- Acrylates such as (2-propenyloxyethyl) oxetane, 3- (2-propenyloxyethyl) -3-ethyloxetane, etc., 3- (methyl Allyloxymethyl) oxetane, 3- (methacryloxymethyl) -2-methyloxa Butane, 3- (methacrylfluorenyloxymethyl) -3-ethyloxetane, 3- (methacrylfluorenyloxymethyl) -2-phenyloxetane Consisting of 3- (2-methacrylfluorenyloxyethyl) oxetane and 3- (2-methacrylfluorenyloxyethyl) -3-ethyloxetane At least one of the group. The polyester amidine (A) according to item 1, 2, or 4 of the scope of the patent application, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3 ', 4,4'-dibenzene Hydrazone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride At least one compound in the group consisting of 1,1,2,3,4-butanetetracarboxylic dianhydride and ethylene glycol bis (anhydrotrimellitate), the diamine is 3,3'- At least one of diaminodiphenylfluorene and bis [4- (3-aminophenoxy) phenyl] fluorene, the polyhydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butane Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis (4-hydroxycyclohexyl) propane, 4 , 4'-Dihydroxydicyclohexyl, tris (2-hydroxyethyl) isocyanurate, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, and 2- (4-hydroxyphenyl) ethanol At least one of the group. The polyester amido acid (A) according to item 2 or 4 of the scope of the patent application, wherein the compound having three or more acid anhydride groups is a styrene-maleic anhydride copolymer. The polyester amido acid (A) according to item 4 of the scope of the patent application, wherein the monohydroxy compound is selected from the group consisting of isopropyl alcohol, benzyl alcohol, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl At least one of the group consisting of oxetane. A photosensitive composition comprising the polyester amidate (A) as described in any one of claims 1 to 10 of the patent application scope, a compound (B) having a polymerizable double bond, and a photopolymerization initiator (C), epoxy compound (D) and additives (E). The photosensitive composition according to item 11 of the scope of patent application, wherein the weight average molecular weight of the polyester amidine (A) is 1,000 to 200,000.