TW201619293A - Photosensitive compositions and usage thereof - Google Patents

Abstract

The present invention concerns a composition containing a polyesteramide acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound and an epoxy curing agent, and a photosensitive composition having features in which the polyesteramide acid is obtained by allowing reaction of tetracarboxylic dianhydride, diamine and a polyhydric hydroxy compound as essential raw material components. The photosensitive composition of the invention is excellent in applicability to a base substrate. A cured film that is particularly excellent in heat resistance and flatness, and excellent also in adhesion to the base substrate such as glass, and transparency can be obtained by using the photosensitive composition of the invention.

Description

Photosensitive composition and its use

The present invention relates to an insulating material that can be used in forming an electronic component, a passivation film in a semiconductor device, a buffer coating film, an interlayer insulating film, or a planarization film, or an interlayer insulating film or a color filter in a display element. A photosensitive composition such as a protective film, a transparent film using the photosensitive composition, and an electronic component including the film.

In the manufacturing step of an element such as a display element, various chemicals such as an organic solvent, an acid, or an alkali solution may be treated, or when the wiring electrode is formed by sputtering, the surface is locally heated to a high temperature. Therefore, a surface protective film may be provided in order to prevent deterioration, damage, and deterioration of the surface of various elements. For these protective films, it is required to be able to withstand various characteristics of various treatments in the manufacturing steps as described above. Specifically, chemical resistance such as heat resistance, solvent resistance, acid resistance, and alkali resistance, water resistance, adhesion to a base substrate such as glass, transparency, scratch resistance, flatness, light resistance, etc. are required. . In the current state of high performance, such as high viewing angle, high-speed response, and high definition, when a color filter protective film is used, a material having improved heat resistance and planarization characteristics is desired. .

The type of the curable composition for forming these protective films can be roughly distinguished from a photosensitive composition and a thermosetting composition. When the film is formed, the thermosetting composition is completely cured by high-temperature heating. Therefore, even if it is heated to a high temperature in the subsequent step, the amount of volatile components generated is small and the heat resistance is excellent. A thermosetting protective film material having such excellent properties has a polyester phthalic acid composition (for example, see Patent Document 1). However, the thermosetting composition cannot form a scribe line at the time of manufacturing the panel division, and a large amount of fine particles of the protective film are generated, so that a high degree of panel cleaning step is required thereafter.

On the other hand, the photosensitive composition contains a polymer or oligomer having a photopolymerizable group or a monomer and a photopolymerization initiator, and undergoes a chemical reaction due to energy of light represented by ultraviolet rays, and is hardened. The photosensitive composition can easily form a scribe line for manufacturing a panel division, and therefore there is an advantage that fine particles of the protective film are not generated, and conversely, compared with the protective film formed of the thermosetting composition, The heat resistance of the protective film formed of the usual photosensitive composition is insufficient.

In recent years, there is a growing demand for a protective film that requires heat resistance, and a photosensitive composition capable of easily forming a scratch line is required to form a protective film having excellent heat resistance.

A photosensitive composition which can form a protective film having a very excellent heat resistance is a polyimine precursor composition (for example, refer to Patent Document 2) and a soluble polyimine composition (for example, refer to Patent Document 3) . However, even in any photosensitive composition, an organic solvent in which the obtained polyimide intermediate precursor composition or soluble polyimine composition is dissolved is also limited, and an organic solvent having a very high polarity is also required.

Examples of the organic solvent having a high polarity such as a solution of a polyimine precursor composition and a soluble polyimine composition include a pyrrolidone type, an anthraquinone type, a formamide type, an acetamide type, a phenol type, a tetrahydrofuran, and a second. Oxane, γ-butyrolactone, and the like.

In particular, when these photosensitive compositions are used as a color filter protective film, if these organic solvents having a high polarity are contained, for example, pigments or dyes contained in pixels of the color filter layer penetrating the substrate are contained. Since the coloring material is eluted, it is difficult to produce a high-quality display element.

In addition, the curable composition and the thermosetting composition are required to have excellent coatability on the base substrate. [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

[Problems to be solved by the invention]

An object of the present invention is to provide a cured film which is excellent in heat resistance and flatness, and which is excellent in heat resistance and flatness, and which is excellent in heat resistance and flatness, and which is excellent in heat resistance and flatness. A composition excellent in coatability on a base substrate further provides an electronic component having the cured film. [Technical means to solve the problem]

The present inventors have made an effort to solve the above problems, and as a result, have found that the object can be attained by the following composition and a cured film obtained by curing the composition, and the present invention has been completed. The composition comprises a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy hardener, which comprises a tetracarboxylic dianhydride and a diamine. It is obtained by the reaction of a compound of a polyvalent hydroxy compound. The present invention includes the following constitutions.

[1] A photosensitive composition which is a composition comprising a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent, characterized in that: The ester valine acid is reacted by a ratio of the following formula (1) and formula (2) in which the X-mol tetracarboxylic dianhydride, the Y-mole diamine, and the Z-mole polyvalent hydroxy compound are reacted. The structural unit represented by the following formula (3) and the structural unit represented by the formula (4) are obtained; the compound having a polymerizable double bond contains two or more polymerizable double bonds per molecule; an epoxy compound Included in each molecule is two to ten epoxy groups, and the weight average molecular weight is less than 3,000; and the total amount of the compound having a polymerizable double bond is from 20 parts by weight to 300 parts by weight relative to 100 parts by weight of the polyester phthalic acid The total amount of the epoxy compound is from 20 parts by weight to 200 parts by weight; 0.2≦Z/Y≦8.0 ·······(1) 0.2≦(Y+Z)/X≦5.0 ···(2) In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and R ² is a two-NH ₂ removal from the diamine. The resulting residue, R ^{3 ,} is a residue obtained by removing two -OH from a polyvalent hydroxy compound.

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

[3] The photosensitive composition according to [2], wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl- One or more of 3-hydroxymethyloxetane.

[4] The photosensitive composition according to [1] or [2] wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000.

[5] The photosensitive composition according to [1] or [2] wherein the tetracarboxylic dianhydride is selected from 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-butyl One or more of an alkyltetracarboxylic dianhydride and an ethylene glycol bis(hydrogen trimellitate).

[6] The photosensitive composition according to [1] or [2] wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-aminophenoxy) One or more of phenyl] hydrazine.

[7] The photosensitive composition according to [1] or [2] wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl and heterotrimerization One or more of tris(2-hydroxyethyl)cyanate.

[8] The photosensitive composition according to [1], wherein the compound having a polymerizable double bond contains 50% by weight or more of dipentaerythritol selected from the total weight of the compound having a polymerizable double bond. One or more of pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, polybasic acid-modified acrylic oligomer, and isomeric cyanuric acid-modified triacrylate.

[9] The photosensitive composition according to [1] or [2] wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester , 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane, 2-[4-(2,3-epoxypropoxy)benzene 2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane with 1,3-bis[4-[ 1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methyl a mixture of ethyl]phenyl]ethyl]phenoxy]-2-propanol, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1 - bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl ether, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2 One or more of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2-bis(hydroxymethyl)-1-butanol.

[10] The photosensitive composition according to [1] or [2] wherein the photopolymerization initiator is selected from the group consisting of α-aminophenylalkylketone, fluorenylphosphine oxide, and oxime ester photopolymerization. More than one of the initiators.

[11] The photosensitive composition according to [1] or [2] wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole.

[12] The photosensitive composition according to [1], wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1, 2, 3, One or more of 4-butane tetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenyl hydrazine; the polyvalent hydroxy compound is 1,4-butanediol; the compound having a polymerizable double bond is selected One or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified acrylic oligomer; and the photopolymerization initiator contains 50% by weight or more based on the total weight of the photopolymerization initiator ,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzhydrylhydrazine), ethyl ketone, 1-[9-ethyl-6-(2-A Benzobenzhydryl)-9-oxazol-3-yl]-, 1-(O-ethylindenyl) and 1,2-propanedione-1-[4-[[4-(2-hydroxyl) More than one of ethoxy)phenyl]thio]phenyl]-2-(O-ethenylhydrazine); the epoxy compound is selected from 2-[4-(2,3-epoxypropoxy)benzene 2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane with 1,3-bis[4-[ 1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methyl Mixture of ethyl]phenyl]ethyl]phenoxy]-2-propanol And 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) One or more of ethyl]phenyl]propane; the epoxy hardener is one or more selected from the group consisting of trimellitic anhydride and 2-undecylimidazole; further containing methyl 3-methoxypropionate and propylene glycol monomethyl One or more of the ether acetates are used as a solvent.

[13] A cured film obtained by the photosensitive composition according to any one of [1] to [12].

[14] A color filter using the cured film according to [13] as a protective film.

[15] A display element using the color filter as described in [14].

[16] A solid-state image pickup element using the color filter as described in [14].

[17] A display element using the cured film according to [13] as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[18] A display element using the cured film according to [13] as a transparent insulating film formed between the transparent electrode and the alignment film.

[19] A touch panel using the cured film as described in [13] as a transparent insulating film formed between electrodes.

[20] A light-emitting diode (LED) light-emitting body using the cured film according to [13] as a protective film. [Effects of the Invention] The photosensitive composition of the preferred embodiment of the present invention is a material which does not require an organic solvent having a high polarity and which can form a cured film which is particularly excellent in heat resistance and flatness, and is used as a color display element. In the case of a color filter protective film, display quality and reliability can be improved. Further, the cured film obtained by the photosensitive composition of the preferred embodiment of the present invention is also balanced in transparency, chemical resistance, adhesion, and sputtering resistance, and has high practicality. In particular, it is effectively used as a protective film for a color filter manufactured by a dyeing method, a pigment dispersion method, an electrodeposition method, and a printing method. Moreover, it can also be used as a protective film of various optical materials and a transparent insulating film.

Photosensitive composition

The photosensitive composition of the present invention is a compound containing polyester phthalic acid, containing two or more polymerizable double bonds per molecule, a photopolymerization initiator, and two to ten rings in each molecule. An epoxy compound having a weight average molecular weight of less than 3,000 and a composition of an epoxy curing agent which is prepared by using a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. The compound obtained by the reaction is characterized in that the compound having a polymerizable double bond is 20 parts by weight to 300 parts by weight, and the epoxy compound is 20 parts by weight to 200 parts by weight based on 100 parts by weight of the polyester phthalic acid. Further, the photosensitive composition of the present invention may further contain other components than the above in the range in which the effects of the present invention are obtained. 1-1. Polyester proline

The polyester phthalic acid is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. More specifically, the X-molar tetracarboxylic dianhydride, the Y-mole diamine, and the Z-mole polyvalent hydroxy compound are reacted at a ratio in which the relationship of the following formula (1) and formula (2) is established. obtain. 0.2≦Z/Y≦8.0 ······· (1) 0.2≦(Y+Z)/X≦5.0 (2) Polyester phthalic acid has a structure represented by the following formula (3) The unit and the structural unit represented by the formula (4).

In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from a tetracarboxylic dianhydride, and is preferably an organic group having 2 to 30 carbon atoms. R ² is a residue obtained by removing two -NH ₂ from a diamine, and is preferably an organic group having 2 to 30 carbon atoms. R ³ is a residue obtained by removing two -OH from a polyvalent hydroxy compound, and is preferably an organic group having 2 to 20 carbon atoms.

At least a solvent is required for the synthesis of the polyester phthalic acid, and the solvent may be directly left to form a liquid or gel-like photosensitive composition in consideration of workability or the like, or the solvent may be removed to take into consideration A solid composition such as portability. Further, the synthesis of the polyester phthalic acid may optionally contain one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer as a raw material, and preferably contains a monohydroxy compound. Further, the synthesis of the polyester proline may be carried out as a raw material, if necessary, in addition to the object of the present invention. Examples of such other raw materials include monoamine-containing amines. 1-1-1. Tetracarboxylic dianhydride

In the present invention, tetracarboxylic dianhydride is used as a material for obtaining polyester phthalic acid. Specific examples of preferred tetracarboxylic dianhydrides include: 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid Dihydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2',3, 3'-diphenylphosphonium tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic acid Dihydride, 2,2',3,3'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[double ( 3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, ethylene glycol bis(hydrogen trimellitate) (trade name; TMEG- 100, New Japan Physicochemical Co., Ltd.), cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, ethane Tetracarboxylic dianhydride and butane tetracarboxylic dianhydride. One or more of these tetracarboxylic dianhydrides can be used.

Among these tetracarboxylic dianhydrides, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride and 3,3',4,4'-diphenyl ether tetra which impart good transparency are more preferable. Carboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, and TMEG-100, especially Preferred are 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride and 1,2,3,4-butyl Alkanetetracarboxylic dianhydride. 1-1-2. Diamine

In the present invention, a diamine is used as a material for obtaining polyester proline. Specific examples of preferred diamines include 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 3,4'-diaminodiphenylguanidine, and bis. [4-(4-Aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[3-(4-aminophenoxy)phenyl ][,(4-(4-Aminophenoxy)phenyl][3-(4-aminophenoxy)phenyl]anthracene, [4-(3-aminophenoxy)phenyl] [3-(4-Aminophenoxy)phenyl]anthracene, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. More than one of these diamines can be used.

Among these diamines, 3,3'-diaminodiphenylanthracene and bis[4-(3-aminophenoxy)phenyl]anthracene which impart good transparency are more preferable, and 3,3'- is particularly preferable. Diaminodiphenylphosphonium. 1-1-3. Polyols

In the present invention, a polyhydroxy compound is used as a material for obtaining polyester proline. Specific examples of preferred polyvalent hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a weight average molecular weight of 1,000 or less, propylene glycol, dipropylene glycol, and tripropylene glycol. Tetrapropylene glycol, polypropylene glycol having a weight average molecular weight of 1,000 or less, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentane Glycol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6 - hexanetriol, 1,2-heptanediol, 1,7-heptanediol, 1,2,7-heptanetriol, 1,2-octanediol, 1,8-octanediol, 3,6 -octanediol, 1,2,8-octanetriol, 1,2-decanediol, 1,9-nonanediol, 1,2,9-nonanetriol, 1,2-decanediol, 1 , 10-decanediol, 1,2,10-nonanetriol, 1,2-dodecanediol, 1,12-dodecanediol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, Tris(2-hydroxyethyl) isocyanate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)fluorene), double Phenol F (bis(4-hydroxyphenyl)methane), 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxybicyclo Group, diethanolamine, and triethanolamine. One or more of these polyvalent hydroxy compounds may be used.

Among these polyvalent hydroxy compounds, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- which are excellent in solubility in a solvent are more preferable. Heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl, and tris(2-hydroxyethyl) isocyanurate The ester is particularly preferably 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. 1-1-4. Monohydroxy compound

In the present invention, a monohydroxy compound can be used as the material for obtaining the polyester proline. By using a monohydroxy compound, the storage stability of the photosensitive composition can be improved. Specific examples of preferred monohydroxy compounds include benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, and diethylene glycol. Alcohol monomethyl ether, diethylene glycol monoethyl ether, hydroxyethyl methacrylate, terpineol, 3-ethyl-3-hydroxymethyl oxetane and dimethylbenzyl methanol (dimethyl Benzyl carbinol). One or more of these monohydroxy compounds may be used.

Among these monohydroxy compounds, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl-3-hydroxymethyl oxetane are more preferable. Consider compatibility in the case where a polyester phthalic acid formed by using these monohydroxy compounds is mixed with an epoxy group-containing polymer, an epoxy compound, and an epoxy hardener, or a photosensitive composition in a color filter For the coating property on the light sheet, it is particularly preferable to use benzyl alcohol as the monohydroxy compound.

The reaction is carried out by containing 0 to 300 parts by weight of a monohydroxy compound, based on 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 weight part - 200 weight part. 1-1-5. Styrene-maleic anhydride copolymer

Further, the polyester phthalic acid used in the present invention may be synthesized by adding a compound having three or more acid anhydride groups to the raw material. By carrying out as described above, transparency can be improved, which is preferable. An example of the compound having three or more acid anhydride groups is exemplified by a styrene-maleic anhydride copolymer. The molar ratio of styrene/maleic anhydride is from 0.5 to 4, preferably from 1 to 3, with respect to the ratio of each component constituting the styrene-maleic anhydride copolymer. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

Specific examples of the styrene-maleic anhydride copolymer include SMA3000P, SMA2000P, and SMA1000P (all trade names; Chuan crude oil chemical company). Among these commercial products, SMA1000P excellent in heat resistance and alkali resistance is particularly preferable.

The styrene-maleic anhydride copolymer is preferably contained in an amount of from 0 to 500 parts by weight based on 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. It is more preferably 10 parts by weight to 300 parts by weight. 1-1-6. Monoamine containing hydrazine

In the synthesis of the polyester valine acid, other raw materials other than the above may be contained as a raw material as needed within the range not impairing the object of the present invention, and examples of such other raw materials include fluorene-containing monoamine.

Specific examples of the preferred fluorene-containing monoamine used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-aminopropylmethyldi Methoxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-aminobutylmethyldiethyl Oxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyldiethoxydecane And m-aminophenyltrimethoxydecane, and m-aminophenylmethyldiethoxydecane. One or more of these monoamine-containing monoamines can be used.

Among these monoamine-containing monoamines, 3-aminopropyltriethoxydecane and p-aminophenyltrimethoxydecane having good acid resistance of the coating film are more preferable, from the viewpoints of acid resistance and compatibility, particularly 3-Aminopropyltriethoxydecane is preferred.

It is preferable to contain 0 to 300 parts by weight of a fluorene-containing monoamine with respect to 100 parts by weight of the total amount of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound. More preferably, it is 5 weight part - 200 weight part. 1-1-7. Solvent used in the synthesis reaction of polyester proline

Specific examples of the solvent used in the synthesis reaction for obtaining polyester proline include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethylene glycol. Alcohol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexane ketone. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, or diethylene glycol methyl ethyl ether is preferable. 1-1-8. Method for synthesizing polyester proline

The method for synthesizing the polyester phthalic acid used in the present invention is to react a tetracarboxylic dianhydride X-mole, a diamine Y-mole, and a polyvalent hydroxy compound Z-mol in the solvent. In this case, X, Y, and Z are preferably set to a ratio at which the relationship between the following formulas (1) and (2) is established between these X, Y, and Z. If it is this range, since the solubility of a polyester valine acid in a solvent is high, the coating property of a composition improves, and as a result, the cured film which is excellent in flatness can be obtained. 0.2≦Z/Y≦8.0 ········(1) 0.2≦(Y+Z)/X≦5.0 ···(2)

In the formula (1), 0.7≦Z/Y≦7.0 is preferable, and 1.0≦Z/Y≦5.0 is more preferable. Further, in the formula (2), 0.5 ≦ (Y + Z) / X ≦ 4.0 is preferable, and 0.6 ≦ (Y + Z) / X ≦ 2.0 is more preferable.

The polyester phthalic acid used in the present invention is an excess of an acid having a hydroxyl group or a hydroxyl group at the terminal under the reaction conditions and using X more than Y+Z. A molecule of the group (-CO-O-CO-). When the reaction is carried out in the constitution of such a monomer, the terminal is subjected to esterification in order to react with an acid anhydride group at the terminal of the molecule, and the above-mentioned monohydroxy compound may be added as needed. The polyester proline obtained by the reaction by adding a monohydroxy compound can improve compatibility with an epoxy compound and an epoxy hardener, and can improve the coatability of the photosensitive composition of the present invention containing these compounds.

Further, when the reaction is carried out in the configuration of the monomer, a fluorene-containing monoamine may be added in order to introduce a decyl group at the terminal end to react with an acid anhydride group at the molecular terminal. When the photosensitive composition of the present invention containing polyester phthalic acid (which is obtained by adding a hydrazine monoamine-containing reaction) is used, the acid resistance of the obtained coating film can be improved. Further, when the reaction is carried out in the configuration of the monomer, a reaction between the monohydroxy compound and the monoamine-containing monoamine may be carried out.

When 100 parts by weight or more of the reaction solvent is used per 100 parts by weight of the total of the tetracarboxylic dianhydride, the diamine, and the polyvalent hydroxy compound, the reaction proceeds smoothly, which is preferable. The reaction is preferably carried out at a temperature of from 40 ° C to 200 ° C for from 0.2 hours to 20 hours.

The order in which the reaction raw materials are added to the reaction system is not particularly limited. That is, any of the following methods may be used: a tetracarboxylic dianhydride, a diamine and a polyhydric hydroxy compound are simultaneously added to a reaction solvent; after dissolving a diamine and a polyhydric hydroxy compound in a reaction solvent, tetracarboxylic dianhydride is added. After the tetracarboxylic dianhydride and the polyvalent hydroxy compound are previously reacted, a diamine is added to the reaction product; or the tetracarboxylic dianhydride and the diamine are previously reacted, and a polyvalent hydroxy compound or the like is added to the reaction product.

In the case of reacting the ruthenium-containing monoamine, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction solution is cooled to 40 ° C or lower, and then the monoamine-containing amine is added at 10 ° C. The reaction is carried out at -40 ° C for 0.1 hour to 6 hours. Moreover, a monohydroxy compound can be added at any point in the reaction.

The polyester phthalic acid synthesized as described above contains the structural unit represented by the formula (3) and the structural unit represented by the formula (4), and the terminal is derived from tetracarboxylic dianhydride as a raw material, and An acid anhydride group, an amine group or a hydroxyl group of an amine or a polyvalent hydroxy compound, or an additive other than these compounds constitutes a terminal. By including such a structure, hardenability becomes favorable.

The weight average molecular weight of the obtained polyester phthalic acid is preferably from 1,000 to 200,000, more preferably from 3,000 to 50,000. If it is in these ranges, flatness and heat resistance will become favorable.

The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 ml/min). Standard polystyrene uses polystyrene with a molecular weight of 645 to 132,900 (for example, Agilent Technologies, Inc., polystyrene calibration kit PL2010-0102), and the column uses PLgel MIXED-D. (Agilent Technologies, Inc.) can be measured using Tetrahydrofuran (THF) as the mobile phase. Further, the weight average molecular weight of the commercially available product in the present specification is a catalogue value. 1-2. Compounds having a polymerizable double bond

The compound having a polymerizable double bond used in the present invention is not particularly limited as long as it has a polymerizable double bond. When the compound having a polymerizable double bond is 100 parts by weight to 300 parts by weight based on 100 parts by weight of the polyester phthalic acid, the residual film ratio after development is improved, which is preferable.

The compound having a polymerizable double bond contained in the photosensitive composition of the present invention may, for example, be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate or triethylene glycol di( Methyl) 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(methyl) Acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin-modified propylene glycol di(meth)acrylate, epichlorohydrin-modified dipropylene glycol di(meth)acrylate, epichlorohydrin-modified tripropylene glycol (Meth) acrylate, epichlorohydrin-modified tetrapropylene glycol di(meth) acrylate, epichlorohydrin-modified polypropylene glycol di(meth) acrylate, trimethylol Propane tri(meth)acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin Trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, glycerol (meth)acrylate, glycerol di(meth)acrylate, glycerol 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, hydroxypivalic acid neopentyl glycol di(meth)acrylate, butyrolactone Hydroxypentovaleric acid neopentyl glycol di(meth)acrylate, diglycerin tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, stearic acid modification Pentaerythritol di(meth) acrylate, dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (methyl) propyl Acid ester, alkyl modified dipentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, butyrolactone modified dipentaerythritol hexa(meth) acrylate, di(meth) acrylate propylene Cyclohexyl ester, bis[(meth)acryloxy neopentyl glycol] adipate, bisphenol A di(meth) acrylate, ethylene oxide modified bisphenol A di(methyl) Acrylate, bisphenol F di(meth) acrylate, ethylene oxide modified bisphenol F di(meth) acrylate, bisphenol S di(meth) acrylate, ethylene oxide modified double Phenol S di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, dicyclopentyl diacrylate, epoxy B Alkyl modified di(meth)acrylate, ethylene oxide modified tris(meth)acrylate, butyrolactone, ethylene oxide modified di(meth)acrylate, butyrolactone, Ethylene oxide modified tris(meth)acrylate, epichlorohydrin modified di(meth)acrylate, tetrabromobisphenol A di(meth)acrylate, triglycerin II Acrylate, neopentyl glycol modified trishydroxymethyl Di(meth)acrylate, isomeric cyanuric acid modified diacrylate, isomeric cyanuric acid modified triacrylate, butyrolactone modified tris[(methyl)propene A methoxyethyl]isomeric cyanurate, a (meth)acrylated isocyanurate, a polybasic acid modified (meth)acrylic acid oligomer, and the like.

The compound having a polymerizable double bond may be used singly or in combination of two or more.

From the viewpoint of heat resistance and chemical resistance, among the compounds having a polymerizable double bond, it is preferred to use trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol. Hexaacrylate, isomeric cyanuric acid modified diacrylate, isomeric cyanuric acid modified triacrylate, polyacid modified (meth)acrylic oligomer, or these mixture.

Trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isomeric cyanuric acid ethylene oxide modified diacrylate, isomeric cyanide As the acid ethylene oxide-modified triacrylate, or a mixture of these, a commercially available product such as the following can be used. A specific example of trimethylolpropane triacrylate is Aronix M-309 (trade name, East Asia Synthetic Co., Ltd.). Specific examples of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate are Aronix M-306 (65% by weight to 70% by weight), and Aronix M-305 (55% by weight to 63% by weight). %), Aronix M-303 (30% to 60% by weight), Aronix M-452 (25% to 40% by weight), and Aronix M- 450 (less than 10% by weight, hereinafter abbreviated as "M-450") (all product names, East Asia Synthetic Co., Ltd., and the content ratio in parentheses are catalogue values of the content ratio of pentaerythritol triacrylate in the mixture). Specific examples of the mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are Aronix M-403 (50% by weight to 60% by weight) and Aronix M-400 (40% by weight - 50% by weight), Aronix M-402 (30% by weight to 40% by weight, hereinafter abbreviated as "M-402"), and Aronix M-404 (30% by weight to 40% by weight) ), Aronix M-406 (25% to 35% by weight), and Aronix M-405 (10% to 20% by weight) (all are trade names, East Asia Synthetic Co., Ltd.) The content in the company and the parentheses is the catalogue value of the content of dipentaerythritol pentaacrylate in the mixture). A specific example of the isomeric cyanuric acid ethylene oxide-modified diacrylate is Aronix M-215 (trade name, East Asia Synthetic Co., Ltd.). A specific example of a mixture of isomeric cyanuric acid ethylene oxide modified diacrylate and isomeric cyanuric acid ethylene oxide modified triacrylate is Aronix M-313 (30% by weight to 40%) (% by weight) and Aronix M-315 (3 wt% to 13 wt%, hereinafter abbreviated as "M-315") (all of which are trade names, East Asia Synthetic Co., Ltd., and the content ratio in parentheses is a mixture) The catalogue of the content of the iso-cyanuric acid-modified diacrylate in the catalogue). Specific examples of the polyacid-modified (meth)acrylic oligomer are Aronix M-510 and Aronix M-520 (both trade names, East Asia Synthetic Co., Ltd.). 1-3. Photopolymerization initiator

The photopolymerization initiator contained in the photosensitive composition of the present invention is not particularly limited as long as it can start polymerization of a composition containing polyester phthalic acid and having a polymerizable double bond. Compounds, photopolymerization initiators, epoxy compounds, and epoxy hardeners.

The photopolymerization initiator contained in the photosensitive composition of the present invention may, for example, be benzophenone, micbutone, 4,4'-bis(diethylamino)benzophenone or xanthene. Ketone, thioxanthone, isopropyl oxa ketone, 2,4-diethyl thia fluorenone, 2-ethyl hydrazine, acetophenone, 2-hydroxy-2-methylpropiophenone, 2 -hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane 1-ketone (for example, IRGACURE 907; trade name; BASF Japan Co., Ltd.), 2-benzyl-2-dimethylamino-1-(4-morpholino) Phenyl)-butanone-1 (for example, IRGACURE 369; trade name; BASF Japan Co., Ltd.), 4-dimethylaminobenzoic acid ethyl ester, 4-dimethyl Isoamyl benzoate, 4,4'-bis(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tris(t-butylperoxycarbonyl)benzol 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzhydrylhydrazine) (for example, IRGACURE OXE-01; trade name; BASF Japan Co., Ltd.), 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-double (trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2' , 4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis (three Chloromethyl)-s-triazine, 2-(4'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di( Ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-all three Pyrazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-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-ethoxyl Carbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked Imidazole, 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-dimethylaminopropyl) Carbazole, 3,6-bis(2-methyl-2-morpholinopropanyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (h5-2, 4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, N-1919, NCI-831, and NCI-930 (all are trade names, ADEKA Co., Ltd.).

The photopolymerization initiator may be used singly or in combination of two or more. From the viewpoint of the transparency and the sensitivity, the photopolymerization initiator is preferably an α-aminophenanone, a mercaptophosphine oxide or an oxime ester photopolymerization initiator.

From the viewpoint of transparency and sensitivity, in the photopolymerization initiator, if 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzylidene fluorene) Or 1,2-propanedione-1-[4-[[4-(2-hydroxyethoxy)phenyl]thio]phenyl]-2-(O-ethenylhydrazine) relative to photopolymerization More preferably, the total weight of the initiator is 20% by weight or more. Moreover, it is more preferable if it is 50 weight% or more. The photopolymerization initiator may also contain only 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine) or 1,2-propanedione. 1-[4-[[4-(2-Hydroxyethoxy)phenyl]thio]phenyl]-2-(O-ethylindenyl). 1-4. Epoxy compound

The epoxy compound used in the present invention contains two to ten epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding an epoxy compound to the photosensitive composition of the present invention, heat resistance can be improved. When the epoxy compound is 20 parts by weight to 150 parts by weight based on 100 parts by weight of the polyester phthalic acid, the flatness is improved, which is preferable.

Preferable examples of the epoxy compound include 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester (for example, Celloxide 2021P; trade name; Daicel 璐(Daicel) Co., Ltd.), 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane (for example, Celloxide 3000) ;trade name; Daicel Co., Ltd.), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane with 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl] 1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol Mixture, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) )]ethyl]phenyl]propane (for example, TECHMORE VG3101L; trade name; Printec), 1,1,1-tris(4-hydroxyphenyl)ethane Glycidyl ether (for example, JER 1032H60; trade name; Mitsubishi Chemical Corporation), 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, 2,2-bis(hydroxymethyl)-1-butanol 1,2-epoxy-4-(2-oxirane a cyclohexane adduct (for example, EHPE-3150; trade name; Daicel Co., Ltd.). 1-5. Epoxy hardener

In the photosensitive composition of the present invention, an epoxy curing agent is used in order to improve flatness and chemical resistance. The epoxy curing agent includes an acid anhydride-based curing agent, an amine-based curing agent, a phenol-based curing agent, an imidazole-based curing agent, a catalyst-type curing agent, and a sensible salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt or a phosphonium salt. The acid generator-based curing agent or the imidazole-based curing agent is preferred from the viewpoint of avoiding the coloration of the cured film and the heat resistance of the cured film.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic anhydrides (for example, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and hexahydrogen). Oral polycarboxylic acid anhydride (for example, phthalic anhydride, trimellitic anhydride, etc.). Among these acid anhydride-based curing agents, trimellitic anhydride and hexahydrotrimellitic anhydride having a good balance between heat resistance and solubility in a solvent are particularly preferable.

Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2,3-dihydro- 1H-pyrrolo[1,2-a]benzimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate. Among these imidazole-based curing agents, 2-undecylimidazole having a good balance between curability and solubility in a solvent is particularly preferable. 1-6. Proportion of polyester phthalic acid, compound having a polymerizable double bond, photopolymerization initiator, epoxy compound, and epoxy hardener

In the photosensitive composition of the present invention, the ratio of the compound having a polymerizable double bond to 100 parts by weight of the polyester phthalic acid is 20 parts by weight to 300 parts by weight. When the ratio of the compound having a polymerizable double bond is in this range, the balance between heat resistance, flatness, chemical resistance, and residual film ratio after development is good. Further, the compound 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 of the present invention, the ratio of the epoxy compound is from 20 parts by weight to 200 parts by weight based on 100 parts by weight of the polyester phthalic acid. When the ratio of the epoxy compound is in this range, the balance between heat resistance and flatness is good. It is more preferable if the epoxy compound is in the range of 20 parts by weight to 150 parts by weight.

The ratio of the epoxy curing agent to the epoxy compound is from 0.1 part by weight to 60 parts by weight based on 100 parts by weight of the epoxy compound and the epoxy curing agent. For example, in the case where the epoxy curing agent is an acid anhydride-based curing agent, the amount of the carboxylic acid anhydride group or the carboxyl group in the epoxy curing agent is preferably 0.1 times equivalent to the epoxy group. Add in 1.5 equivalents. At this time, the carboxylic anhydride group was calculated at a divalent value. When the carboxylic anhydride group or the carboxyl group is added in an amount of from 0.15 to 0.8 equivalents, the chemical resistance is further improved, and thus it is more preferable. 1-7. Other ingredients

Various additives may be added to the photosensitive composition of the present invention to improve coating uniformity, adhesion, and resolution. The additives may, for example, be solvents, anionic, cationic, nonionic, fluorine or lanthanide leveling agents/surfactants, phthalocyanine coupling agents and the like, and hindered phenols, hindered amines, and phosphorus. An antioxidant such as a sulfur compound or a 1,2-quinonediazide compound. 1-7-1. Solvent

A solvent may also be added to the photosensitive composition of the present invention. The solvent to be added arbitrarily in the photosensitive composition of the present invention is preferably a solvent which can dissolve a polyester phthalic acid, a compound having a polymerizable double bond, an epoxy compound, or an epoxy curing agent. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxylate. Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , propyl pyruvate, methyl acetate 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 acetate, ethylene glycol monobutyl ether Ester, 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 solvents, or a mixture of two or more of these solvents. 1-7-2. Surfactant

In the photosensitive composition of the present invention, a surfactant may also be added to improve coating uniformity. Specific examples of the surfactant include: Polyflow No. 45, Polyflow KL-245, Polyflow No. 75, Polyflow No. .90, Polyflow No. 95 (all of which are trade names; Kyoeisha Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Di Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Di Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of which are trade names; Japan) BYK Chemie Japan Co., Ltd., KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of which are trade names; Shin-Etsu Chemical Co., Ltd.) , Surflon SC-101, Surflon KH-40, Surflon S611 (above) All are trade names; AGC Seimi Chemical Co., Ltd., Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (all of which are trade names; Neos Co., Ltd.) ), EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF-801, EFTOP EF- 802 (all of the above are trade names; Mitsubishi Material Co., Ltd.), 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, Meijia (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 (all of which are trade names; Di Aisheng (DIC) Co., Ltd., TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, Digog TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all of the above are trade names, Japan Evonik Degu Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, halothane Sulfonate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene Ethyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene hard Aliphatic ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan Stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, Polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkylbenzene sulfonate, and alkyl diphenyl ether disulfonate. It is preferred to use at least one selected from these compounds.

Among these surfactants, if selected from BYK306, BYK342, BYK346, KP-341, KP-358, KP-368, Surflon S611, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac F-559, Meijiafa (Megafac) RS-72-k, Megafac DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, At least one of the fluoroalkyl sulfonate, the fluoroalkyltrimethylammonium salt, and the fluoroalkylaminosulfonate is preferred because the coating uniformity of the photosensitive composition is high.

The content of the surfactant in the photosensitive composition of the present invention is preferably 0.01% by weight to 10% by weight based on the total amount of the photosensitive composition. 1-7-3. Adhesion enhancer

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

As such an adhesion improving agent, a coupling agent of a decane type, an aluminum type, or a titanate type can be used, for example. Specific examples thereof include 3-glycidoxypropyl dimethyl ethoxy decane, 3-glycidoxy propyl methyl diethoxy decane, and 3-glycidoxy propyl trimethoxy decane. (e.g., Sila-Ace S510; trade name; Jie Enzhi Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (for example, Saras (Sila) -Ace)S530; trade name; Jie Enzhi Co., Ltd., 3-mercaptopropyltrimethoxydecane (for example, Sila-Ace S810; trade name; Jenzhi Co., Ltd.), glycidyloxy a hydrolyzate of propyl decane (for example, CoatOSil MP200; trade name; Momentive Performance Materials Co., Ltd.), a decane coupling agent, acetonitrile alkoxide, aluminum isopropoxide, etc. A titanate coupling agent such as an aluminum coupling agent or tetraisopropylbis(dioctylphosphite) titanate.

Among these adhesion promoters, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving adhesion.

The content of the adhesion improving agent is preferably 10% by weight or less based on the total amount of the photosensitive composition. On the other hand, it is preferably 0.01% by weight or more. 1-7-4. Antioxidants

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

An antioxidant such as a hindered phenol type, a hindered amine type, a phosphorus type or a sulfur type compound may be added to the photosensitive composition of the present invention. Among them, a hindered phenol type is preferred from the viewpoint of weather resistance. Specific examples can be cited: Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, Easy Ginos (Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Yi Gannos (Irganox) 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Yi Gan Irganox 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Yi Zhanno Irganox 565DD, Irganox 295 (both trade names; BASF Japan Co., Ltd.), ADK STAB AO-20, Eddie Costabo (ADK STAB) AO-30, ADIK STAB AO-50, ADK STAB AO-60,迪科斯塔波 (ADK STAB) AO-70, Addison Costa wave (ADK STAB) AO-80 (both trade names; manufactured by ADEKA (ADEKA) Ltd.). Among them, Irganox 1010 and ADK STAB AO-60 are more preferable.

An antioxidant is added in an amount of 0.1% by weight to 5% by weight based on the total amount of the photosensitive composition. 1-7-5. 1,2-quinonediazide compound

The photosensitive composition of the present invention may further contain a 1,2-quinonediazide compound from the viewpoint of further improving the resolution.

The 1,2-quinonediazide compound is present in 1,2-benzopyrene diazidosulfonate, 1,2-naphthoquinonediazide sulfonate, 1,2-benzopyrene diazide Sulfonamide, and 1,2-naphthoquinonediazidesulfonamide. Specific examples include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate and 2,3,4-trihydroxybenzophenone-1,2 -naphthoquinonediazide-5-sulfonate (NT-200; trade name; East Asia Synthetic Industrial Co., Ltd.), 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide 4-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2',4,4'-tetrahydroxydiphenyl Ketone-1,2-naphthoquinonediazide-4-sulfonate, 2,2',4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid Ester, 2,3,3',4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,3',4-tetrahydroxybenzophenone- 1,2-naphthoquinonediazide-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-naphthoquinone Azide-4-sulfonate, 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) Alkane-1,2-naphthoquinonediazide-4-sulfonate, tris(p-hydroxyphenyl)methane-1,2-naphthoquinonediazide-5-sulfonate, 1,1,1-three (p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide-4-sulfonate, 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazide -5-sulfonate; bis(2,3,4-trihydroxyphenyl)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-trihydroxyphenyl)propane-1,2-naphthoquinonediazide-5-sulfonate; 1,1,3-three (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-naphthoquinonediazide-5-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl] -1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-4-sulfonate, 4,4'-[1-[4-[1-[4 -hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate; bis(2,5-dimethyl-4) -hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, bis(2,5-di Methyl-4-hydroxyphenyl)-2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3',3'-tetramethyl-1,1 '-Spirulina-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3',3'- Tetramethyl-1,1'-spirobiguan-5,6,7,5',6',7'-hexanol-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ,4-trimethyl-7,2',4'-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate, and 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate.

In particular, it is more preferably selected from the group consisting of 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate and 2,3,4-trihydroxybenzophenone- 1,2-naphthoquinonediazide-5-sulfonate, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene Bisphenol-1,2-naphthoquinonediazide-4-sulfonate, and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl At least one of phenyl]ethylidene]bisphenol-1,2-naphthoquinonediazide-5-sulfonate.

To the total amount of the photosensitive composition, 0.01% by weight to 0.5% by weight of a 1,2-quinonediazide compound is added and used. 1-7-6. Other additives

The photosensitive composition of the present invention may further contain a polymer (hereinafter referred to as "radical copolymerized polymer") which is a radical polymerizable compound represented by the following formula (6) A1) A radically polymerizable compound (a2) having an alkoxyalkylalkyl group and a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group are subjected to radical copolymerization. (R ⁸ is hydrogen or methyl, R ⁹ to R ¹² are alkyl groups having 1 to 5 carbon atoms, R ¹³ is an alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 10, and n is 1 to 150. Integer) 1-7-6-1. Radical polymerizable compound (a1)

Since the radically polymerizable compound (a1) represented by the formula (6) functions as a surfactant, the (a1) is used as a raw material, and the radical copolymer polymer acts as a surfactant, even if The flatness, the adhesion to the base substrate, and the coatability can be improved without adding a surfactant. By adding the radically polymerizable compound (a1), the radical copolymer polymer becomes easy to surface on the surface of the film.

In the present invention, in the radically polymerizable compound (a1) represented by the formula (6), R ⁸ is preferably hydrogen or a methyl group, R ⁹ to R ¹² are a methyl group, and R ¹³ is a carbon number of 1 to 10. An alkyl group, m is an integer of from 1 to 5, and n is a compound of an integer of from 1 to 150. More preferably, R ⁸ is a methyl group, R ⁹ to R ¹² are a methyl group, R ¹³ is a butyl group, m is 3, and n is an integer of 1 to 150, and more preferably n is an integer of 30 to 70. The compound is particularly preferably a compound in which n is an integer of from 50 to 70. The radically polymerizable compound (a1) represented by the formula (6) preferably has a weight average molecular weight of 500 to 8,000.

The radically polymerizable compound (a1) can be produced by a known method. Moreover, a commercial item can also be used. For example, FM-0711, FM-0721, FM-0725 (all are trade names; Jie Enzhi Co., Ltd.) and the like. 1-7-6-2. Radical polymerizable compound having an alkoxyalkyl group (a2)

In the present invention, a radically polymerizable compound (a2) having an alkoxyalkyl group is used to obtain a raw material of the radical copolymer polymer. The preferred radically polymerizable compound (a2) is selected from the group consisting of 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, 3- (Meth) propylene methoxy propyl methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy One or more groups consisting of decane and p-styryltrimethoxydecane. Among these radically polymerizable compounds, 3-(meth)acryloxypropyltrimethoxydecane and 3-(meth)acryloxypropyltriethoxydecane are preferred because of their good flatness. By using (a2), transparency, chemical resistance, and the like are improved. Further, the adhesion to the substrate is improved by the decane coupling effect. 1-7-6-3. A radically polymerizable compound having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group (a3)

In the present invention, a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group is used to obtain a raw material of the radical copolymer polymer. A preferred radically polymerizable compound (a3) is selected from the group consisting of glycidyl (meth)acrylate, glycidyl ether of 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid, and 4-hydroxyphenylvinyl group. More than one group consisting of ketones. (a3) It functions as a crosslinking agent of a polymer, and contributes to improvement of heat resistance, chemical resistance, etc.. 1-7-6-4. Method for producing radical copolymerized polymer

The radical polymerizable polymer is a radical polymerizable compound (a1) represented by the formula (6), a radically polymerizable compound (a2) having an alkoxyalkyl group, and an epoxy group, a carboxyl group, or a hydroxybenzene group. At least one radical polymerizable compound (a3) of the group is obtained by radical copolymerization. The method for producing the radical copolymerized polymer is not particularly limited, and the radical polymerizable compound can be heated in the presence of a radical initiator to produce a radical copolymerized polymer. As the radical initiator, an organic peroxide, an azo compound or the like can be used. The reaction temperature of the radical copolymerization is not particularly limited, but is usually in the range of 50 ° C to 150 ° C. The reaction time is also not particularly limited, but is usually in the range of 1 hour to 48 hours. Further, the reaction can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure.

The solvent used in the radical copolymerization reaction is preferably a solvent which dissolves the produced polymer. Specific examples of the solvent are ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxylate. Methyl acetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxy-2-methylpropionate, 2- Ethyl hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , propyl pyruvate, methyl acetate 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 acetate, ethylene glycol monobutyl ether Ester, 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 solvents, or a mixture of two or more of these solvents.

In the radical copolymerized polymer used in the present invention, the solvent used in the polymerization may be directly left to form a radical copolymerized polymer solution in consideration of workability or the like, or the solvent may be removed for consideration. A solid-state radical copolymerized polymer such as portability.

When the weight average molecular weight of the radical copolymerized polymer obtained by gel permeation chromatography (GPC) analysis using polystyrene standards is in the range of 1,000 to 50,000, the film formation property of the film is good. It is preferred. Further, when the weight average molecular weight is in the range of 2,500 to 20,000, the flatness of the film is good, and it is more preferable. Further, when the weight average molecular weight is in the range of 2,500 to 15,000, flatness and chemical resistance are good, and it is particularly preferable.

0.1 to 5 parts by weight of other additives are added to the total amount of the photosensitive composition and used. 1-8. Preservation of photosensitive components

When the photosensitive composition of the present invention is stored in the range of -30 ° C to 25 ° C, the stability with time of the composition is improved, which is preferable. If the storage temperature is -20 ° C to 10 ° C, there is no precipitate and it is more preferable. 2. A cured film obtained from a photosensitive composition

The photosensitive composition of the present invention can be obtained by mixing a polyester phthalic acid, a compound having a polymerizable double bond, an epoxy compound, and an epoxy curing agent, and further selecting as needed according to the target characteristics. These compounds are uniformly mixed and dissolved by adding a solvent, a coupling agent, a surfactant, and other additives.

When the photosensitive composition prepared as described above (in the case of a solid state without a solvent, dissolved in a solvent) is applied onto the surface of the substrate, and the solvent is removed by, for example, heating, a coating film can be formed. 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 to apply the photosensitive composition to the surface of the substrate. Next, the coating film is heated (prebaked) by 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 from 70 ° C to 150 ° C, from 5 minutes to 15 minutes in the case of an oven, and from 1 minute to 5 minutes in the case of using a hot plate.

Thereafter, the coating film is irradiated with ultraviolet rays by a mask that is interposed in a desired pattern shape. Suitably, the amount of ultraviolet radiation is from 5 mJ/cm ² to 1000 mJ/cm ² in terms of i-rays. The photosensitive composition irradiated with ultraviolet rays is polymerized by a compound having a polymerizable double bond to form a three-dimensional crosslinked body, and is insolubilized in an alkaline developing solution.

Next, the coating film is immersed in an alkaline developing solution by spray development, spray development, liquid coating development, immersion development, or the like, and an unnecessary portion is dissolved and removed. Specific examples of the alkaline developing solution 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 or tetraethylammonium hydroxide. Further, an appropriate amount of methanol, ethanol, a surfactant, or the like may be added to the alkaline developer to be used.

Finally, in order to completely cure the coating film, a cured film can be obtained by heat treatment at 180 ° C to 250 ° C, preferably 200 ° C to 250 ° C, and if it is an oven, 30 minutes to 90 minutes, if It is a heating plate for 5 minutes to 30 minutes.

When the cured film obtained as described above is heated, 1) the polyamic acid moiety of the polyester phthalic acid is dehydrated and cyclized to form a quinone bond, and 2) the carboxylic acid and the ring containing the polyester phthalic acid Since the polymer of an oxy group reacts with a high molecular weight, it is very strong, and is excellent in transparency, heat resistance, chemical resistance, flatness, adhesion, light resistance, and sputtering resistance. Therefore, the cured film of the present invention is effective as a protective film for a color filter, and a color filter can be used to manufacture a liquid crystal display element or a solid-state image sensor. Further, the cured film of the present invention is effective as a transparent insulating film formed between the TFT and the transparent electrode or a transparent insulating film formed between the transparent electrode and the alignment film, in addition to the protective film for the color filter. Further, the cured film of the present invention is effective even as a protective film for an LED illuminator. [Examples]

Next, the present invention will be specifically described by way of Synthesis Examples, Reference Examples, Examples, and Comparative Examples, but the present invention is not limited by these examples. First, a polyester proline solution containing a reaction product of a tetracarboxylic dianhydride, a diamine, a polyvalent hydroxy compound, or the like (Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4) was synthesized as follows. [Synthesis Example 1] Synthesis of Polyester Amidinic Acid Solution (A1)

In a four-necked flask equipped with a stirrer, methyl 3-methoxypropionate (hereinafter abbreviated as "MMP") and 3,3',4,4'-diphenyl were subjected to dehydration purification under the following weight. The ether tetracarboxylic dianhydride (hereinafter abbreviated as "ODPA"), 1,4-butanediol, and benzyl alcohol were stirred at 130 ° C for 3 hours under a nitrogen stream. MMP 446.96 g ODPA 183.20 g 1,4-butanediol 31.93 g benzyl alcohol 25.54 g

Thereafter, the reaction liquid was cooled to 25° C., and 3,3′-diaminodiphenyl hydrazine (hereinafter abbreviated as “DDS”) and MMP were added in the following weight, and the mixture was stirred at 20° C. to 30° C. for 2 hours. The mixture was stirred at 115 ° C for 1 hour. DDS 29.33 g MMP 183.04 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A1) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 4,200. [Synthesis Example 2] Synthesis of Polyester Amidinic Acid Solution (A2)

In a four-necked flask equipped with a stirrer, MMP, ODPA, 2,2-bis(4-hydroxycyclohexyl)propane and benzyl alcohol which were subjected to dehydration purification were sequentially added under the following weight, under a dry nitrogen stream at 130 ° C. Stir for 3 hours. MMP 445.93 g ODPA 153.02 g 2,2-bis(4-hydroxycyclohexyl)propane 71.15 g benzyl alcohol 21.34 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 24.50 g MMP 174.07 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A2) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A2) was 4,000. [Synthesis Example 3] Synthesis of Polyester Amidinic Acid Solution (A3)

In a four-necked flask equipped with a stirrer, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMEA") and 1,2,3,4-butane tetracarboxylate which were subjected to dehydration purification were sequentially added in the following weights. Acid dianhydride (hereinafter abbreviated as "BT-100"), 2,2-bis(4-hydroxycyclohexyl)propane, and benzyl alcohol were stirred at 130 ° C for 3 hours under a nitrogen stream. PGMEA 444.22 g BT-100 122.90 g 2,2-bis(4-hydroxycyclohexyl)propane 89.47 g benzyl alcohol 26.83 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 30.80 g MMP 185.78 g [Z/Y=3.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (A3) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A3) was 3,800. [Synthesis Example 4] Synthesis of Polyester Amidinic Acid Solution (A4)

In a four-necked flask equipped with a stirrer, MMP, ODPA, and 2,2-bis(4-hydroxycyclohexyl)propane which were subjected to dehydration purification were sequentially placed under the following weight, and dried under a nitrogen stream at 130 ° C. Stir for hours. MMP 483.84 g ODPA 187.78 g 2,2-bis(4-hydroxycyclohexyl)propane 72.75 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 130 ° C for 2 hours. DDS 9.47 g MMP 146.16 g [Z/Y=7.9, (Y+Z)/X=0.6]

The solution was cooled to room temperature to obtain a 30 wt% solution (A4) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (A4) had a weight average molecular weight of 3,500. [Synthesis Example 5] Synthesis of Polyester Amidinic Acid Solution (B1)

In a four-necked flask equipped with a stirrer, PGMEA, BT-100, and SMA1000P (trade name; styrene-maleic anhydride copolymer, Chuan crude oil chemical co., Ltd.) which were subjected to dehydration purification were sequentially placed under the following weights. 1,4-butanediol and benzyl alcohol were stirred at 125 ° C for 3 hours under a stream of dry nitrogen. PGMEA 481.37 g BT-100 34.47 g SMA1000P 164.11 g 1,4-butanediol 10.45 g benzyl alcohol 50.17 g

Thereafter, the reaction liquid was cooled to 25° C., DDS and PGMEA were added in the following weight, stirred at 20° C. to 30° C. for 2 hours, and then stirred at 125° C. for 2 hours. DDS 10.80 g PGMEA 148.63 g [Z/Y=2.7, (Y+Z)/X=0.9]

The solution was cooled to room temperature to obtain a 30 wt% solution (B1) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B1) was 10,000. [Synthesis Example 6] Synthesis of Polyester Amidinic Acid Solution (B2)

PGMEA, BT-100, SMA1000P, 1,4-butanediol, and benzyl alcohol which were subjected to dehydration purification were sequentially placed in a four-necked flask equipped with a stirrer under the following conditions, and dried at 125 ° C under a nitrogen stream. Stir for 3 hours. PGMEA 494.87 g BT-100 33.80 g SMA1000P 160.93 g 1,4-butanediol 10.25 g benzyl alcohol 61.49 g

Thereafter, the reaction liquid was cooled to 25° C., DDS and PGMEA were added in the following weight, stirred at 20° C. to 30° C. for 2 hours, and then stirred at 125° C. for 2 hours. DDS 3.53 g PGMEA 135.13 g [Z/Y=8.0, (Y+Z)/X=0.8]

The solution was cooled to room temperature to obtain a 30 wt% solution (B2) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the obtained polymer (B2) had a weight average molecular weight of 9,000. [Synthesis Example 7] Synthesis of Polyester Amidinic Acid Solution (B3)

In a four-necked flask equipped with a stirrer, PGMEA, diethylene glycol ethyl methyl ether (hereinafter abbreviated as "EDM"), ODPA, SMA1000P, and 1,4- Butanediol and benzyl alcohol were stirred at 120 ° C for 3 hours under a stream of dry nitrogen. PGMEA 504.00 g EDM 96.32 g ODPA 47.7 g SMA1000P 144.97 g 1,4-butanediol 9.23 g benzyl alcohol 55.40 g

Thereafter, the reaction liquid was cooled to 25 ° C, DDS and MMP were added in the following weight, stirred at 20 ° C to 30 ° C for 2 hours, and then stirred at 120 ° C for 2 hours. DDS 12.72 g EDM 29.68 g [Z/Y=2.0, (Y+Z)/X=1.0]

The solution was cooled to room temperature to obtain a 30 wt% solution (B3) of pale yellow transparent polyester phthalic acid. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (B3) was 21,000. [Comparative Synthesis Example 1] Synthesis of Polylysine Solution (C1)

In a four-necked flask equipped with a stirrer, MMP, DDS, and ODPA which were subjected to dehydration purification were sequentially placed in the following weight, and stirring was continued at 20 ° C to 30 ° C, and as a result, a slightly gray slurry was obtained, and aggregation was impossible. Proline solution. MMP 765.00 g DDS 60.02 g ODPA 74.98 g [Z/Y=0, (Y+Z)/X=1.0] [Comparative Synthesis Example 2] Synthesis of Polylysine Solution (C2)

In a four-necked flask equipped with a stirrer, N-methyl-2-pyrrolidone (hereinafter abbreviated as "NMP"), DDS, and ODPA, which were subjected to dehydration purification, were sequentially added under the following weight, at 20 ° C to 30 ° C. After stirring for 2 hours, the mixture was stirred at 120 ° C for 2 hours. NMP 765.00 g DDS 60.02 g ODPA 74.98 g [Z/Y=0, (Y+Z)/X=1.0]

The solution was cooled to room temperature to obtain a 15% by weight solution (C2) of a thick yellow transparent polyamine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C2) was 8,000. [Comparative Synthesis Example 3] Synthesis of Polylysine Solution (C3)

In a four-necked flask equipped with a stirrer, MMP, 3-aminopropyltriethoxysilane (hereinafter abbreviated as "S330"), DDS, and ODPA, which were subjected to dehydration purification, were sequentially placed in the following weights, at 20 Stirring was carried out for 2 hours at °C to 30 °C. MMP 630.00 g S330 138.25 g DDS 15.51 g ODPA 116.24 g [Z/Y=0, (Y+Z)/X=0.2]

The solution was cooled to room temperature to obtain a 30 wt% solution (C3) of a thick yellow transparent polylysine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C3) was 2,000. [Comparative Synthesis Example 4] Synthesis of Polylysine Solution (C4)

In a four-necked flask equipped with a stirrer, MMP, hexylamine, DDS, and ODPA which were subjected to dehydration purification were sequentially placed in the following weight, and stirring was continued at 20 to 30 ° C to obtain a slightly yellow slurry. Polyisamic acid solution could not be obtained. MMP 630.00 g Hexylamine 87.53 g DDS 21.48 g ODPA 161.00 g [Z/Y=0, (Y+Z)/X=0.2] [Comparative Synthesis Example 5] Synthesis of Polylysine Solution (C5)

In a four-necked flask equipped with a stirrer, NMP, hexylamine, DDS, and ODPA which were subjected to dehydration purification were sequentially placed under the following weight, and stirred at 20 ° C to 30 ° C for 2 hours. NMP 630.00 g hexylamine 87.53 g DDS 21.48 g ODPA 161.00 g [Z/Y=0, (Y+Z)/X=0.2]

The solution was cooled to room temperature to obtain a 30 wt% solution (C5) of a thick yellow transparent polylysine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C5) was 1,500. [Comparative Synthesis Example 6] Synthesis of Polylysine Solution (C6)

In a four-necked flask equipped with a stirrer, NMP, hexylamine, DDS, and ODPA which were subjected to dehydration purification were sequentially placed in the following weight, and stirred at 20 ° C to 30 ° C for 2 hours, and then at 120 ° C. 2 Stir for hours. NMP 630.00 g hexylamine 51.01 g DDS 62.59 g ODPA 156.39 g [Z/Y=0, (Y+Z)/X=0.5]

The solution was cooled to room temperature to obtain a 30 wt% solution (C6) of a thick yellow transparent polyamine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C6) was 1,600. [Comparative Synthesis Example 7] Synthesis of Polylysine Solution (C7)

In a four-necked flask equipped with a stirrer, dehydrated and purified EDM, benzylamine, DDS, and ODPA were placed in the following order, and stirring was continued at 20 to 30 ° C to obtain a slightly yellow slurry. A polyproline solution could not be obtained. EDM 630.00 g benzylamine 53.42 g DDS 61.90 g ODPA 154.67 g [Z/Y=0, (Y+Z)/X=0.5] [Comparative Synthesis Example 8] Synthesis of Polyproline Solution (C8)

In a four-necked flask equipped with a stirrer, NMP, benzylamine, DDS, and ODPA which were subjected to dehydration purification were sequentially placed in the following weight, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then at 120 ° C. Stir for 2 hours. NMP 630.00 g benzylamine 53.42 g DDS 61.90 g ODPA 154.67 g [Z/Y=0, (Y+Z)/X=0.5]

The solution was cooled to room temperature to obtain a 30 wt% solution (C8) of a thick yellow transparent polyamine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C8) was 1,200. [Comparative Synthesis Example 9] Synthesis of Polylysine Solution (C9)

In a four-necked flask equipped with a stirrer, NMP, benzylamine, DDS, and ODPA which were subjected to dehydration purification were sequentially placed in the following weight, and the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then at 120 ° C. Stir for 2 hours. NMP 630.00 g benzylamine 90.94 g DDS 21.08 g ODPA 157.98 g [Z/Y=0, (Y+Z)/X=0.2]

The solution was cooled to room temperature to obtain a 30 wt% solution (C9) of a thick yellow transparent polyamine. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (C9) was 2,000.

Then, the polymer is a radically polymerizable compound (a1) represented by the formula (6), a radically polymerizable compound (a2) having an alkoxyalkyl group, and The radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group and a hydroxyphenyl group is subjected to radical copolymerization. [Synthesis Example 8] Synthesis of a free radical copolymerized polymer (D) solution

In a four-necked flask equipped with a stirrer, dehydrated and purified EDM as a polymerization solvent and FM-0721 as a radical polymerizable compound (a1) were charged in the following weight (in the formula (6), R ⁸ - R ¹² is a methyl group, R ¹³ is a butyl group, m = 3, n = 66, a weight average molecular weight: 5,000, Jengen Co., Ltd., and a radically polymerizable compound (a2) having an alkoxyalkyl group 3-methylpropenyloxypropyltrimethoxydecane, glycidyl methacrylate as a radically polymerizable compound (a3) having at least one of an epoxy group, a carboxyl group, and a hydroxyphenyl group, further in the following weight 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601; trade name; Wako Pure Chemical Industries Co., Ltd.) as a polymerization initiator, under a dry nitrogen stream, 90 Stirring was carried out for 2 hours at °C. EDM 40.00 g FM-0721 0.20 g glycidyl methacrylate 8.00 g 3-methylpropenyloxypropyltrimethoxydecane 11.80 g V-601 2.00 g

The solution was cooled to room temperature to obtain a 33.3 wt% solution of the radical copolymer polymer. A portion of the solution was sampled and the weight average molecular weight was determined by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained radical copolymerized polymer was 7,800. [Example 1]

A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 80.0 g of the polyester phthalic acid solution (A1) obtained in Synthesis Example 1 and 45.0 g were charged as a polymerizable double in the flask. M402 of the bond compound, 3.0 g of OXE-01 as a photopolymerization initiator, 30.0 g of VG3101L as an epoxy compound, 4.5 g of trimellitic anhydride as an epoxy curing agent (hereinafter abbreviated as "TMA"), 2.9 g 3-glycidoxypropyltrimethoxydecane as an additive (for example, Sila-Ace S510; trade name; Jenzhi Co., Ltd.) and 0.3 g of Eddie Costap (ADK) STAB) AO-60 (trade name; ADEKA Co., Ltd.), 255.2 g of dehydrated purified MMP and 77.8 g of EDM as a solvent, and stirred at room temperature for 3 hr to make it uniform Dissolved in the ground. Next, 0.1 g of Megafac F-556 (trade name; Di Ai Sheng (DIC) Co., Ltd.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered by a membrane filter (0.2 μm) to prepare a coating liquid. .

The photosensitive composition was spin-coated on a glass substrate at 600 rpm for 10 seconds, and prebaked on a hot plate at 120 ° C for 2 minutes. Secondly, in the air, using the proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.), the light below 350 nm is cut off by a wavelength cut-off filter, and g-rays, h-rays, and I-ray and expose. The exposure amount was measured using an integrated light meter UIT-102 (trade name; oxtail (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; oxtail (USHIO) Co., Ltd.) to be 200 mJ/cm. ² . The coating film after exposure was subjected to liquid-coating development for 60 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide, and the coating film was washed with pure water for 20 seconds, and then dried by a hot plate at 100 ° C for 2 minutes. Further, post-baking was carried out in an oven at 230 ° C for 30 minutes to obtain a cured film having a film thickness of 1.5 μm.

The cured film obtained as described above was evaluated for the residual film ratio, heat resistance, transparency, resolution, and flatness after development. [Method for evaluating residual film rate after development]

The film thickness before development and the film thickness after development were measured using a step, surface roughness, and fine shape measuring device (trade name; P-16, KLA TENCOR Co., Ltd.), and the residual film ratio after development was calculated ( Film thickness after development × 100% / film thickness before development). [Method for evaluating heat resistance]

After the obtained glass substrate with a cured film was reheated at 250 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following calculation formula. The film thickness was measured using P-16. The case where the residual film rate after heating was 95% or more was evaluated as "○", and the case where the residual film ratio after heating was less than 95% was evaluated as "x". Residual film rate = (film thickness after heating / film thickness before heating) × 100 [Evaluation method of transparency]

In the obtained glass substrate with a cured film, the transmittance at a light having a wavelength of 400 nm of only the cured film was measured by an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, Japan Optical Co., Ltd.). The case where the transmittance was 95% or more was evaluated as "○", and the case where the transmittance was less than 95% was evaluated as "x".

Next, the photosensitive composition was spin-coated on a glass substrate at 600 rpm for 10 seconds, and dried on a hot plate at 120 ° C for 2 minutes. Next, in the air, a mask with a line pattern of 50 μm wide is used, and a proximity exposure machine TME-150PRC is used to cut off light of 350 nm or less through a wavelength cut filter, and g rays and h rays are taken out. I-rays were exposed with an exposure gap of 10 μm. The exposure amount was measured by an integrated light amount meter UIT-102 and a light receiver UVD-365PD, and was set to 200 mJ/cm ² . The exposed coating film was subjected to liquid-coating development for 60 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide to remove the unexposed portion. The developed coating film was washed with pure water for 20 seconds, and then dried by a hot plate at 100 ° C for 2 minutes. Further, it was post-baked in an oven at 230 ° C for 30 minutes to obtain a glass substrate having a patterned transparent body.

Regarding the cured film obtained as described above, the properties were evaluated for the analytical properties. [Analytical evaluation method]

The obtained glass substrate with a pattern-like transparent body was observed with a 1,000-fold optical microscope, and the resolution of the line pattern corresponding to the mask size of 100 μm was evaluated. The case where the line pattern was analyzed was evaluated as "○", and the case where the analysis was not performed was evaluated as "X".

Next, the photosensitive composition was spin-coated at 600 rpm for 10 seconds on a substrate of a pigment dispersion color filter (hereinafter abbreviated as "CF") using a resin black matrix having a maximum step difference of about 0.8 μm, and heated at 120 ° C. Dry on the plate for 2 minutes. Secondly, in the air, a mask with a line pattern of 50 μm wide is used, and a proximity exposure machine TME-150PRC (trade name; Topcon Co., Ltd.) is used, and a wavelength cut filter is used. The light below nm is turned off, and g-rays, h-rays, and i-rays are taken out, and exposure is performed at an exposure gap of 100 μm. The exposure amount was measured using an integrated light meter UIT-102 (trade name; oxtail (USHIO) Co., Ltd.) and a light receiver UVD-365PD (trade name; oxtail (USHIO) Co., Ltd.) to be 200 mJ/cm. ² . The exposed coating film was subjected to liquid-coating development for 60 seconds using a 0.4% by weight aqueous solution of tetramethylammonium hydroxide to remove the unexposed portion. The developed coating film was washed with pure water for 20 seconds, and then dried by a hot plate at 100 ° C for 2 minutes. Further, it was post-baked in an oven at 230 ° C for 30 minutes to obtain a glass substrate having a patterned transparent body. Next, the coating liquid was spin-coated on a glass substrate and a color filter substrate at 600 rpm for 10 seconds, and then prebaked on a hot plate at 120 ° C for 2 minutes to form a coating film. Thereafter, the film was cured by heating at 230 ° C for 30 minutes in an oven to obtain a cured film having a film thickness of 1.5 μm.

Regarding the cured film obtained as described above, the properties were evaluated for flatness. [Evaluation method of flatness]

The step of the surface of the cured film of the obtained color filter substrate with a cured film was measured using a step, surface roughness, and fine shape measuring device (trade name; P-16, KLA TENCOR Co., Ltd.) . The case where the maximum value of the step difference between the R, G, and B pixels including the black matrix (hereinafter, abbreviated as "maximum step difference") is less than 0.16 μm is evaluated as "○", and the case where 0.16 μm or more is evaluated as "×". . Further, the color filter substrate to be used is a pigment-dispersed color filter (hereinafter abbreviated as "CF") using a resin black matrix having a maximum step difference of about 0.70 μm. [Examples 2 to 8]

According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) shown in Table 1, and the photosensitive composition was obtained. In addition, regarding the abbreviations of the additives in Tables 1 to 3, S510 represents an adhesion improver Sila-Ace S510 (trade name; Jie Enzhi Co., Ltd.), and AO-60 represents an antioxidant Edikes. ADB STAB AO-60 (trade name; ADEKA), NT-200 means 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide -5-sulfonate (trade name; Toyo Synthetic Industrial Co., Ltd.), F-556, which is a surfactant, Megafac F-556 (trade name; Di Ai Sheng (DIC) Co., Ltd.).

Table 1 Unit [g] [Example 9 to Example 12]

According to the method of Example 1, the components were mixed and dissolved in the ratio (unit: g) of Table 2 to obtain a photosensitive composition.

Table 2 Unit [g] [Comparative Example 1 to Comparative Example 7]

According to the method of Example 1, the components were mixed and dissolved in the ratio (unit: g) of Table 3 to obtain a photosensitive composition.

table 3 Unit [g]

In the following, the evaluation results of the cured films of Examples 1 to 8 are collectively shown in Table 4, and the evaluation results of the cured films of Examples 9 to 12 are collectively shown in Table 5, and Comparative Example 1 is shown. The evaluation results of the cured film of Comparative Example 7 are collectively shown in Table 6.

Table 4

table 5

Table 6

According to the results shown in Tables 4, 5, and 6, the cured films of Examples 1 to 8 are excellent in heat resistance, transparency, and flatness, and further include all aspects of residual film ratio and resolution after development. Get balanced. The cured films of Examples 9 to 12 were inferior to Examples 1 to 8 except that the average value of the flatness was slightly larger. On the other hand, the cured film of Comparative Example 1 and Comparative Example 3 to Comparative Example 7 required a polar solvent, and all the evaluation items were not "○" except for the cured films of Comparative Example 3 and Comparative Example 7. All of the properties of the cured film of Comparative Example 1 were inferior. Further, the cured film of Comparative Example 2 was inferior in transparency, resolution, and flatness, and the cured film of Comparative Example 4 was inferior in heat resistance, and the cured film of Comparative Example 5 was inferior in heat resistance and resolution, and further, the cured film of Comparative Example 6 was flat. Poor sex. As described above, all of the characteristics can be satisfied in the case of using the polyester phthalic acid obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. [Industrial availability]

The cured film obtained from the photosensitive composition of the present invention is excellent in heat resistance, transparency, flatness, and the like as an optical material, and can be used as a color filter, an LED light-emitting element, and a light-receiving element from this point of view. A protective film of various optical materials or the like, and a transparent insulating film formed between the TFT and the transparent electrode and between the transparent electrode and the alignment film.

no

no

no

Claims (20)

A photosensitive composition comprising a polyester phthalic acid, a compound having a polymerizable double bond, a photopolymerization initiator, an epoxy compound, and an epoxy curing agent, characterized in that: the polyester The proline is obtained by reacting X-molar tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyvalent hydroxy compound at a ratio established by the relationship of the following formula (1) and formula (2). a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); wherein the compound having a polymerizable double bond contains two or more polymerizable double bonds per molecule; The epoxy compound contains two to ten epoxy groups per molecule, and the weight average molecular weight is less than 3,000; the total amount of the compound having a polymerizable double bond is 100 parts by weight relative to the polyester phthalic acid 20 parts by weight to 300 parts by weight, the total amount of the epoxy compound is 20 parts by weight to 200 parts by weight; 0.2≦Z/Y≦8.0 ·······(1) 0.2≦(Y+Z)/ X≦5.0 ···(2) In the formulae (3) and (4), R ¹ is a residue obtained by removing two -CO-O-CO- from the tetracarboxylic dianhydride, and R ² is two from the diamine. a residue formed by -NH ₂ , and R ³ is a residue obtained by removing two -OH from the polyvalent hydroxy compound. The photosensitive composition according to claim 1, wherein the raw material component of the polyester phthalic acid further comprises a monohydroxy compound. The photosensitive composition according to claim 2, wherein the monohydroxy compound is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl More than one type of -3-hydroxymethyloxetane. The photosensitive composition according to claim 1 or 2, wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000. The photosensitive composition according to claim 1 or 2, wherein the tetracarboxylic dianhydride is selected from the group consisting of 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 One or more of butane tetracarboxylic dianhydride and ethylene glycol bis(hydrogen trimellitate). The photosensitive composition according to claim 1 or 2, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-aminobenzene) One or more of oxy)phenyl]anthracenes. The photosensitive composition according to claim 1 or 2, wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 4,4'-dihydroxydicyclohexyl and One or more of tris(2-hydroxyethyl) cyanurate. The photosensitive composition according to claim 1 or 2, wherein the compound having a polymerizable double bond contains 50% by weight or more based on the total weight of the compound having a polymerizable double bond. a kind selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, polybasic acid modified acrylic oligomer, and isomeric cyanuric acid modified triacrylate the above. The photosensitive composition according to claim 1 or 2, wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexyl Methyl ester, 1-methyl-4-(2-methyloxiranyl)-7-oxabicyclo[4.1.0]heptane, 2-[4-(2,3-epoxypropoxy) Phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane with 1,3-bis[4] -[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1- Mixture of methylethyl]phenyl]ethyl]phenoxy]-2-propanol, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1 , 1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane, 1,1,1-tris(4-hydroxyphenyl)ethane triglycidyl Ether, 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione One or more of 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol. The photosensitive composition according to claim 1 or 2, wherein the photopolymerization initiator is selected from the group consisting of an α-aminophenanone, a mercaptophosphine oxide, and an oxime ester. More than one type of photopolymerization initiator. The photosensitive composition according to claim 1 or 2, wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. The photosensitive composition according to claim 1, wherein the tetracarboxylic dianhydride is selected from the group consisting of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride and 1,2, More than one of 3,4-butanetetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenylphosphonium; the polyvalent hydroxy compound is 1,4-butanediol; The compound of the polymerizable double bond is one or more selected from the group consisting of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polybasic acid-modified acrylic oligomer; the photopolymerization relative to the total weight of the photopolymerization initiator The initiator contains 50% by weight or more selected from 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoguanidinopurine), ethyl ketone, 1- [9-Ethyl-6-(2-methylbenzhydryl)-9-oxazol-3-yl]-, 1-(O-ethylindenyl) and 1,2-propanedione-1 One or more of [[4-[[4-(2-hydroxyethoxy)phenyl]thio]phenyl]-2-(O-ethinyl)); the epoxy compound is selected from 2-[ 4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl] Phenyl]propane and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4-[1-[4-(2,3- Glycidoxy)phenyl a mixture of 1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol and 2-[4-(2,3-epoxypropoxy)phenyl]-2-[ One or more of 4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane; the epoxy hardener is selected from trimellitic anhydride and 2 One or more of undecyl imidazole; further containing one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate as a solvent. A cured film obtained by the photosensitive composition according to any one of claims 1 to 12. A color filter using the cured film as described in claim 13 as a protective film. A display element using the color filter of claim 14 of the patent application. A solid-state image pickup element using the color filter described in claim 14 of the patent application. A display element using the cured film as described in claim 13 as a transparent insulating film formed between the thin film transistor and the transparent electrode. A display element using the cured film as described in claim 13 as a transparent insulating film formed between the transparent electrode and the alignment film. A touch panel using the cured film as described in claim 13 as a transparent insulating film formed between electrodes. A light-emitting diode illuminant using the cured film described in claim 13 as a protective film.