TW201542622A - Thermosetting compositions, cured films, color filters, liquid crystal display elements, solid-state imaging elements and LED luminous bodies - Google Patents

Abstract

A thermosetting composition contains a polyester amide acid, an epoxy group-containing polymer, an epoxy compound and an epoxy curing agent, characterized in that the polyester amide acid is obtained by a reaction in which tetracarboxylic dianhydride, diamine, and a polyvalent hydroxy compound serve as essential raw-material components, and that the epoxy group-containing polymer is obtained by a reaction in which glycidyl (meth)acrylate and bifunctional (meth)acrylate serve as essential raw-material components. The thermosetting composition of the invention is excellent in coating properties. A cured film formed by the thermosetting composition of the invention is particularly excellent in light resistance and flatness, and is also excellent in heat resistance, chemical resistance such as solvent resistance, acid resistance and alkali resistance, etc., water resistance, adhesion to an underlying substrate such as glass, transparency and scratch resistance.

Description

Thermosetting composition, cured film, color filter, liquid crystal display element, solid-state imaging element, and light-emitting diode illuminator

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 color filter in a liquid crystal display element. A thermosetting composition such as a protective film for a sheet, a transparent film using the thermosetting composition, and an electronic component including the film.

In the manufacturing steps of an element such as a liquid crystal display element, various chemical treatments such as an organic solvent, an acid, and an alkali solution may be performed, or when a wiring electrode is formed by sputtering, the surface may be 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, and scratch resistance are required. Injury, applicability, flatness, light resistance, etc. In addition, in the current state of promoting high performance such as high viewing angle, high-speed response, and high definition of a liquid crystal display device, when used as a color filter protective film, a material having improved planarization characteristics is desired.

Regarding light resistance, it has heretofore been important to perform ultraviolet (UV) ozone treatment for surface cleaning of a protective film. However, in recent years, in the color filter protective film for a transverse electric field mode, in order to improve the coating property of a photosensitive spacer, it becomes necessary to perform higher-efficiency ultraviolet ozone treatment, and increase polymerization. In the ultraviolet exposure step such as a photopolymerization step such as a Polymer Sustained Alignment (PSA) mode or a photo-alignment step of an alignment film, light resistance is a very important characteristic.

As a protective film material having such excellent properties, there are a polyaminic acid composition containing ruthenium (see Patent Document 1) and a polyester phthalic acid composition (see Patent Document 2 and Patent Document 3). The polyamine composition containing ruthenium is a material which is extremely excellent in flatness, but has disadvantages such as insufficient heat resistance and poor alkali resistance. The polyester phthalic acid composition of Patent Document 2 has a drawback that flatness and heat resistance are not sufficient. The polyester phthalic acid composition of Patent Document 3 is a material excellent in flatness, heat resistance, and chemical resistance, but has disadvantages in that light resistance is not sufficient, and transparency is lowered in an ultraviolet ozone treatment or an ultraviolet exposure step. . Therefore, as the protective film material, any of the above materials does not sufficiently satisfy light resistance, flatness, heat resistance, chemical resistance, and other characteristics.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-291150

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-105264

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-156546

An object of the present invention is to provide 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, and coating property. In particular, it is a cured film excellent in flatness and light resistance, and an electronic component including a composition that provides the cured film.

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, an epoxy group-containing polymer, and an epoxy hardener obtained by a reaction of a compound containing a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound. The epoxy group-containing polymer is obtained by reacting a glycidyl (meth)acrylate with a bifunctional (meth) acrylate as a raw material component.

The present invention includes the following constitutions.

[1] A thermosetting composition which is a composition comprising a polyester phthalic acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent, characterized in that the polyester lysine is By using tetracarboxylic dianhydride, diamine, and polyhydroxy compound It is obtained by reacting a necessary raw material component; the polyester proline is obtained by the following formula (1) and formula by using X-mole tetracarboxylic dianhydride, Y-mole diamine, and Z-mole polyvalent hydroxy compound. The ratio of the relationship of (2) is obtained by a reaction, and has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4); and the epoxy group-containing polymer is (meth)acrylic acid. The glycidyl ester and the bifunctional (meth) acrylate are obtained by reacting a necessary raw material component, and the weight average molecular weight is 1,000 to 50,000; the epoxy compound contains 2 to 10 epoxy groups per molecule, and the weight average The molecular weight is less than 3,000; the total amount of the epoxy group-containing polymer and the epoxy compound is from 20 parts by weight to 400 parts by weight relative to 100 parts by weight of the polyester phthalic acid, relative to the epoxy group-containing polymer and epoxy The total amount of the compound is 100 parts by weight, and the epoxy hardener is 0.1 parts by weight to 60 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 removed from the diamine. The resulting residue, R ^{3 ,} is a residue obtained by removing two -OH groups from the polyvalent hydroxy compound.

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

[3] The thermosetting 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 kinds of -3-hydroxymethyloxetane.

[4] The thermosetting composition according to [1] or [2] wherein the raw material component of the polyester phthalic acid further comprises a styrene-maleic anhydride copolymer.

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

[6] The thermosetting composition according to [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).

[7] The thermosetting composition according to [1] or [2] wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-aminophenoxyl) One or more kinds of phenyl) fluorene.

[8] The thermosetting 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 One or more of 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate.

[9] The thermosetting composition according to [1] or [2] wherein the bifunctional (meth) acrylate is selected from the group consisting of ethylene glycol di(meth)acrylate and diethylene glycol di(a) Acrylate, 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricycloanthracene One or more kinds of alkane dimethanol di(meth)acrylate.

[10] The thermosetting composition according to [1] or [2] wherein the epoxy group-containing polymer further comprises, by the raw material component, a glycidyl (meth)acrylate and a bifunctional ( A radically polymerizable monomer other than the compound of the group consisting of methyl acrylates is obtained by a reaction.

[11] The thermosetting composition according to [10], wherein the radically polymerizable monomer other than the compound selected from the group consisting of glycidyl (meth)acrylate and bifunctional (meth)acrylate The body is selected from methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, vinyltrimethoxydecane, ethylene Triethoxy decane, (meth) propylene methoxypropyl-tris-trimethyl hydrazine Alkoxydecane, (meth) propylene oxirane organopolyoxy siloxane, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydro hydrazine (meth) acrylate Base ester, γ-butyrolactone (meth) acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, (meth)acrylic acid-2,2,2-trifluoroethyl One or more of an ester, (meth)acrylic acid, and 4-hydroxyphenyl vinyl ketone.

[12] The thermosetting composition according to [1] or [2] wherein the epoxy compound is selected from 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexyl Ester, 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- a mixture of (2,3-epoxypropoxyphenyl)-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol, and 2-[4-(2,3- One kind of glycidoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane the above.

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

[14] The thermosetting 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 kinds of 4-butane tetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenyl hydrazine; the polyvalent hydroxy compound is 1,4-butanediol; and the epoxy group-containing polymer The reaction is carried out by using glycidyl methacrylate, diethylene glycol dimethacrylate and tetrahydrofurfuryl methacrylate as raw materials. The obtained copolymer having a weight average molecular weight of 1,000 to 50,000; the epoxy compound is 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester; and the epoxy hardener is selected from the group consisting of trimellitic anhydride And one or more types of 2-undecylimidazole; and one or more types selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate are used as a solvent.

[15] A cured film obtained by the thermosetting composition according to any one of [1] to [14].

[16] A color filter using the cured film according to [15] as a protective film.

[17] A liquid crystal display element using the color filter according to [16].

[18] A solid-state image pickup element using the color filter according to [16].

[19] A liquid crystal display element using the cured film according to [15] as a transparent insulating film formed between a thin film transistor (TFT) and a transparent electrode.

[20] A liquid crystal display element using the cured film according to [15] as a transparent insulating film formed between the transparent electrode and the alignment film.

[21] A light-emitting diode (LED) light-emitting body using the cured film according to [15] as a protective film.

The thermosetting composition of the preferred embodiment of the present invention is flat and When a material which is particularly excellent in light resistance is used as a color filter protective film of a color liquid crystal display element, display quality and reliability can be improved. Further, the cured film obtained by heating the thermosetting composition of the preferred embodiment of the present invention is also balanced in transparency, chemical resistance, adhesion, and sputter 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.

Thermosetting composition

The thermosetting composition of the present invention contains polyester proline (obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components), and contains Epoxy group-containing polymer (obtained by reacting glycidyl (meth)acrylate and bifunctional (meth) acrylate as essential raw material components), epoxy compound And a composition of an epoxy curing agent, wherein the epoxy compound is 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid, and 100 parts by weight of the epoxy group-containing polymer. The epoxy hardener is from 0.1 part by weight to 60 parts by weight. Further, the thermosetting 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)

The polyester phthalic acid has a structural unit represented by the following formula (3) and a 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- groups from 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 groups from the 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 valine acid, and the solvent may be directly left to form a liquid or gel-like thermosetting composition in consideration of workability or the like, or the solvent may be removed for consideration. It is a solid composition such as handling property. Further, the synthesis of the polyester valine acid may contain, as a raw material, one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer, and preferably 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 and 2,2',3,3'-benzophenonetetracarboxylic acid II. Anhydride, 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 Anhydride, 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 four A carboxylic acid dianhydride and a 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'-diaminodiphenyl fluorene, 3,3'-diaminodiphenyl fluorene, 3,4'-diaminodiphenyl fluorene, 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]indole, [4-(3-aminophenoxy)phenyl][ 3-(4-Aminophenoxy)phenyl]indole, and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. One or more 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, tripropylene glycol, and tetra Propylene 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-pentane Alcohol, 1,5-pentanediol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexane Alcohol, 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-triol, 1,2-dodecanediol, 1,12-dodecanediol, glycerol, trimethylol Propane, pentaerythritol, dipentaerythritol, tris(2-hydroxyethyl) isocyanurate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyl) Phenyl) bis), bisphenol F (bis(4-hydroxyphenyl)methane), diethanolamine, and triethanolamine. One or more of these polyvalent hydroxy compounds can 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, and tris(2-hydroxyethyl) isocyanurate, 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 thermosetting composition can be improved. Specific examples of preferred monohydroxy compounds include methanol, ethanol, 1-propanol, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and dipropylene glycol monoethyl ether. , dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, phenol, borneol, maltol, Linalol, terpineol, dimethyl benzylcarbinol and 3- Ethyl-3-hydroxymethyloxetane. One or more of these monohydroxy compounds can be used.

Among these monohydroxy compounds, isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, or 3-ethyl-3-hydroxymethyl oxetane is more preferred. Consider compatibility between a polyester phthalic acid formed by using these monohydroxy compounds and an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent, or a thermosetting composition in 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 preferably carried out by containing 0 parts by weight to 300 parts by weight of a monohydroxy compound per 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. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. Regarding the ratio of each component constituting the styrene-maleic anhydride copolymer, the molar ratio of styrene/maleic anhydride is from 0.5 to 4, preferably from 1 to 3. Further, 1 or 2 is more preferable, and 1 is particularly preferable.

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

Preferably, it is a combination with a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound. 100 parts by weight of the styrene-maleic anhydride copolymer is contained in an amount of from 0 part by weight to 500 parts by weight. More preferably, it is 10 weight part - 300 weight part.

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, and from the viewpoint of acid resistance and compatibility, it is particularly preferable. 3-Aminopropyltriethoxydecane.

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 may be Listed diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether Acid ester, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamidine amine. 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. When it is in this range, since the solubility of the polyester valine acid in a solvent is high, the coating property of a composition improves, and it turns out that 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 a component having an amine group or a hydroxyl group at the terminal under the condition that X is excessively used with respect to Y+Z under the reaction conditions. The molecule is more excessively formed to have an acid anhydride group (-CO-O-CO-) at the terminal. 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 phthalic acid 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 thermosetting 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 thermosetting composition of the present invention containing polyester phthalic acid (which is obtained by adding a monoamine-containing monoamine) 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 added.

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. It is preferred to carry out the reaction 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. In addition, the weight average molecular weight of the commercial item in this specification is a catalogue value.

1-2. Epoxy-containing polymer

The epoxy group-containing polymer used in the present invention is obtained by reacting a glycidyl (meth)acrylate and a bifunctional (meth) acrylate as essential raw material components. The epoxy group-containing polymer is not particularly limited as long as it has good compatibility with other components forming the thermosetting composition of the present invention. Further, the bifunctional (meth) acrylate which is reacted with glycidyl (meth)acrylate may be one type or two or more types.

The thermosetting composition of the present invention containing an epoxy group-containing polymer obtained by using one type of glycidyl (meth)acrylate as a raw material monomer has the advantage that the transparency of the cured film obtained therefrom When it is high, the transparency in the ultraviolet ozone treatment step or the ultraviolet exposure step can be suppressed from being lowered. From the viewpoint of flatness, heat resistance, and chemical resistance, it is preferred to contain 40 parts by weight to 99 parts by weight of glycidyl (meth)acrylate in all monomers which are raw materials of the epoxy group-containing polymer. .

Preferable examples of the bifunctional (meth) acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate. 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate. These examples are preferable because the compatibility of the epoxy group-containing polymer obtained by the reaction with glycidyl (meth)acrylate with the polyester phthalic acid becomes good. From the viewpoint of flatness, heat resistance, and chemical resistance, it is preferred to contain 1 part by weight to 30 parts by weight of a bifunctional (meth) acrylate in all monomers which are raw materials of the epoxy group-containing polymer. .

The monomer which becomes a raw material of the epoxy group-containing polymer may also be selected from the group consisting of A radical polymerizable monomer other than the group of the glycidyl (meth)acrylate and the bifunctional (meth)acrylate is used as a raw material component. In the present specification, such a monomer is referred to as "other radical polymerizable monomer". From the viewpoint of exhibiting the characteristics of the other radical polymerizable monomer without impairing the effects of the present invention, it is preferred to contain 0 parts by weight of all monomers which are raw materials of the epoxy group-containing polymer. 40 parts by weight of other radical polymerizable monomer.

Specific examples of the other radical polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, and (meth)acrylic acid ring. Hexyl ester, 2-hydroxyethyl (meth)acrylate, 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, Vinyl trimethoxy decane, vinyl triethoxy decane, (meth) acryloxypropyl-tris-trimethyl decyloxy decane, (meth) propylene decyloxy organopolyoxane, Dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-butyrolactone (meth) acrylate, N-cyclohexyl Maleimide, N-phenylmaleimide, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylic acid, and 4-hydroxyphenyl vinyl ketone.

The other radical polymerizable monomer may be one type or two or more types.

The weight average molecular weight of the epoxy group-containing polymer is preferably from 1,000 to 50,000, more preferably from 3,000 to 20,000. If the molecular weight is in these ranges, sufficient flatness, heat resistance, and chemical resistance are obtained.

1-2-1. Solvent used in the synthesis reaction of the epoxy group-containing polymer

The synthesis of the epoxy group-containing polymer obtained by reacting glycidyl (meth)acrylate with a bifunctional (meth) acrylate as an essential raw material component requires at least a solvent.

Specific examples of the solvent used in the polymerization reaction for obtaining the epoxy group-containing polymer include diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and diethyl ether. Glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ring Hexanone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide. Among these solvents, propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, and diethylene glycol methyl ethyl ether are preferable.

These solvents may be used singly or in combination of two or more kinds. Further, if it is a ratio of 30% by weight or less based on the total amount of the solvent, a solvent other than the solvent may be used in combination.

1-2-2. Method for synthesizing epoxy group-containing polymer

The method for synthesizing the epoxy group-containing polymer is not particularly limited, but is preferably a radical polymerization in a solution using a solvent. When 100 parts by weight or more of the reaction solvent is used with respect to 100 parts by weight of the total of the glycidyl (meth)acrylate, the bifunctional (meth) acrylate, and other radically polymerizable monomers used as needed, The reaction proceeds smoothly, which is preferable. The polymerization temperature is not particularly limited as long as it is a temperature at which radicals are sufficiently generated from the polymerization initiator to be used, and is usually in the range of 50 ° C to 150 ° C. The polymerization time is also not particularly limited, and is usually in the range of 1 hour to 24 hours. Moreover, the polymerization can be carried out under any pressure of pressure, reduced pressure or atmospheric pressure. get on.

As the synthesis of the epoxy group-containing polymer, a known polymerization initiator can be used. Examples of the polymerization initiator include a compound which generates a radical by heat, an azo initiator such as azobisisobutyronitrile, and a peroxide initiator such as benzamidine peroxide. In the radical polymerization reaction, a chain transfer agent such as thioglycolic acid may be added in an appropriate amount in order to adjust the molecular weight of the produced copolymer.

The epoxy group-containing polymer may be used as a solvent for the epoxy compound solution in consideration of handling properties, etc., and may be removed to form a solid ring in consideration of handling properties and the like. Oxygen compound.

1-3. Epoxy compound

The epoxy compound used in the present invention contains 2 to 10 epoxy groups per molecule and has a weight average molecular weight of less than 3,000. By adding an epoxy compound to the thermosetting composition of the present invention, flatness can be improved. When the epoxy compound is contained in an amount of from 1 part by weight to 30 parts by weight per 100 parts by weight of the epoxy group-containing polymer, flatness is improved, which is preferable.

Preferable examples of the epoxy compound are preferably a phenol novolak type epoxy compound, a cresol novolak type epoxy compound, a glycidyl ether type epoxy compound, a bisphenol A novolak type epoxy compound, an aliphatic polyglycidyl ether compound, Or a cyclic aliphatic epoxy compound. Commercially available products as described below can be used for the epoxy compounds.

A glycidyl ether type epoxy compound having 2 to 10 epoxy groups per molecule and having a weight average molecular weight of less than 3,000 is exemplified by: Tekmo (TECHMORE) VG3101L (trade name; Printec Co., Ltd.), EHPE-3150 (trade name; Daicel Co., Ltd.), EPPN-501H, EPPN-502H (all are trade names; Japan Chemical Pharmaceutical Co., Ltd.), JER 1032H60 (trade name; Mitsubishi Chemical Corporation). Examples of the cyclic aliphatic epoxy compound include Celloxide 2021P and Celloxide 3000 (all trade names; Daicel Co., Ltd.). Examples of the bisphenol A novolac type epoxy compound include JER 157S65 and JER 157S70 (all trade names; Mitsubishi Chemical Corporation). Examples of the phenol novolac type epoxy compound include EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER 152, and JER 154 (both trade names; Mitsubishi Chemical Corporation). Examples of the cresol novolak type epoxy compound include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (both trade names; Nippon Kayaku Co., Ltd.).

1-4. Epoxy hardener

In the thermosetting 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, methylhexahydroortho-benzene). An aromatic polycarboxylic acid anhydride (for example, phthalic anhydride or trimellitic anhydride) or a styrene-maleic anhydride copolymer, such as dicarboxylic anhydride or hexahydrotrimellitic anhydride. 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.

1-5. Proportion of polyester phthalic acid, epoxy group-containing polymer, epoxy compound, and epoxy hardener

In the thermosetting composition of the present invention, the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is from 20 parts by weight to 400 parts by weight based on 100 parts by weight of the polyester phthalic acid. When the ratio of the total amount of the epoxy group-containing polymer and the epoxy compound is in this range, the balance between flatness, heat resistance, chemical resistance, and adhesion is good. The total amount of the epoxy group-containing polymer and the epoxy compound is more preferably in the range of 50 parts by weight to 300 parts by weight.

The ratio of the epoxy hardener to the total amount of the epoxy group-containing polymer and the epoxy compound is 100 parts by weight based on the total amount of the epoxy group-containing polymer and the epoxy compound, and the epoxy hardener is 0.1 weight. Parts ~ 60 parts by weight. 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 in terms of the epoxy group. Add in a manner equivalent to 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 equivalents to 0.8 equivalents, the chemical resistance is further improved, which is more preferable.

1-6. Other ingredients

In the thermosetting composition of the present invention, various additives may be added to improve coating uniformity and adhesion. Examples of the additives include solvent, anionic, cationic, nonionic, fluorine- or lanthanide leveling agents/surfactants, adhesion promoters such as decane coupling agents, hindered phenols, hindered amines, and phosphorus. An antioxidant such as a sulfur compound.

1-6-1. Solvent

A solvent may also be added to the thermosetting composition of the present invention. The solvent to be arbitrarily added to the thermosetting composition of the present invention is preferably a solvent which can dissolve a polyester phthalic acid, an epoxy group-containing polymer, an epoxy compound, or an epoxy curing agent. Specific examples of the solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, acetone, 2-butanone, ethyl acetate, Butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid Butyl ester, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropionic acid Methyl ester, 2-hydroxy-2-methylpropionic acid Ethyl ester, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetamidine Methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, dioxane, ethylene glycol, Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, Diethylene glycol monomethyl ether, diethylene glycol 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, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, toluene, xylene, γ-butyrolactone, and N, N- Dimethylacetamide. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

1-6-2. Surfactant

In the thermosetting 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, and Polyflow No. 90, Polyflow No. 95 (all of the above trade names; Kyoei Chemical Co., Ltd.), Disperbyk 161, Disperbyk 162, Diss Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 170, Disperbyk 180, Diss Disperbyk 181, Disperbyk 182, BYK300, BYK306, BYK310, BYK320, BYK330, BYK342, BYK346, BYK361N, BYK-UV3500, BYK-UV3570 (all of which are trade names; 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 (all of which are trade names; AGC Seimi Chemical Co., Ltd.), Fudge ( 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 which are trade names; Mitsubishi Material shares) Ltd.), Megafac F-171, Megafac F-177, Megafac F-410, Megafac F-430, Megafac F-444, Meijia Method (Megafac) F-472SF, Megafac F-475, Megafac F-477, Megafac F-552, Megafac F-553, Megafac F -554, Megafac F-555, Megafac F-556, Megafac F-558, Megafac R-30, Megafac R-94, Meijiafa (Megafac) RS-75, Meijia Method (Megafac) RS-72-K, Megafac RS-76-NS (all of which are trade names; Di Aisheng (DIC) Co., Ltd.), Tegatron 4000 (TEGO Twin) 4000, Di Gaozhen ( TEGO Twin) 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, Digao TEGO Rad 2200N, TEGO Rad 2250N (all of the above are trade names, Evonik-Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluorine Alkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl Trimethylammonium salt, fluoroalkylamine sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene Oleoyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearic acid Ester, polyoxyethylene laurylamine, mountain Alcoholic anhydride laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitol Anhydride palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene sulfonate, and alkyl diphenyl ether disulfonic acid salt. 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, Fujit (Ftergent) 710FS, Ftergent 650A, Megafac F-477, Megafac F-556, Megafac RS-72-k, TEGO Twin 4000, a fluoroalkylbenzenesulfonate, a fluoroalkylcarboxylate, a fluoroalkyl polyoxyethylene ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate In at least one type, the coating uniformity of the thermosetting composition is high, which is preferable.

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

1-6-3. Adhesion enhancer

The thermosetting 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-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxydecane. For example, Sila-Ace S510; trade name; JNC Co., Ltd., 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (such as Sila-Ace) S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxydecane (for example, Sila-Ace S810; trade name; JNC Co., Ltd.) and other decane-based coupling agent, acetamidine An aluminum-based coupling agent such as aluminum alkoxide diisopropoxide or a titanate coupling agent such as tetraisopropylbis(dioctylphosphite) titanate.

Among these adhesion promoters, 3-glycidoxypropyltriethoxysulfonium The alkane is preferred because it has a large effect of improving the adhesion.

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

1-6-4. Antioxidants

The thermosetting 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 thermosetting composition of the present invention. Among them, a hindered phenol type is preferred from the viewpoint of weather resistance. Specific examples include Irganox 1010, Irganox FF, Irganox 1035, Irganox 1035FF, and Easy Ganos ( Irganox) 1076, Irganox 1076FD, Irganox 1076DWJ, Irganox 1098, Irganox 1135, Yi Gannos ( Irganox) 1330, Irganox 1726, Irganox 1425 WL, Irganox 1520L, Irganox 245, Easy Ganos (Irganox) 245FF, Irganox 245DWJ, Irganox 259, Irganox 3114, Irganox 565, Easy Ginos (Irganox) 565DD, Irganox 295 (both trade names; BASF Japan Co., Ltd.), ADX STAB AO-20, Eddie Costap ( ADK STAB) AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80 (both trade names; ADEKA). Among them, Irganox 1010 and ADK STAB AO-60 are more preferable.

To the total amount of the thermosetting composition, 0.1 part by weight to 5 parts by weight of an antioxidant is added and used.

1-6-7. Other additives

In the case where the polyester phthalic acid does not contain a styrene-maleic anhydride copolymer as a raw material, a styrene-maleic anhydride copolymer may be added as another component.

1-7. Preservation of thermosetting composition

When the thermosetting 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 thermosetting composition

The thermosetting composition of the present invention can be obtained by mixing a polyester phthalic acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy curing agent, and further depending on the target characteristics. These compounds are uniformly mixed and dissolved by selectively adding a solvent, a coupling agent, a surfactant, and other additives.

When the thermosetting 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, the solvent is removed by, for example, heating or the like, and a coating film can be formed. . A conventionally known method such as a spin coating method, a roll coating method, a dipping method, or a slit coating method can be used to apply the thermosetting composition to the surface of the substrate. Second, use a hot plate or oven The film is heated (prebaked). 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 a hot plate. Thereafter, in order to harden 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, it is carried out for 30 minutes to 90 minutes. 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 of the polyester phthalic acid and the epoxy group are contained. The polymer is polymerized and polymerized, and 3) the epoxy group-containing polymer is hardened and polymerized, so it is very strong, and has transparency, heat resistance, chemical resistance, flatness, adhesion, and light resistance. Excellent in sputter 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]

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 the examples. First, a polyester proline solution containing a reaction product of a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound was synthesized as follows (Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4).

[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.

Thereafter, the reaction liquid was cooled to 25 ° C, and 3,3'-diaminodiphenyl hydrazine (hereinafter abbreviated as "DDS") and MMP were added under 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.

[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 part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the obtained polymer (A1) had a weight average molecular weight of 4,200.

[Synthesis Example 2] Synthesis of Polyester Amidinic Acid Solution (A2)

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"), SMA1000P (trade name; styrene-maleic anhydride copolymer, Chuan crude oil Co., Ltd.), 1,4-butanediol, benzyl alcohol, in dry nitrogen The mixture was stirred at 125 ° C for 3 hours under running.

Thereafter, the reaction liquid was cooled to 25 ° C, and 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.

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

The solution was cooled to room temperature to obtain a 30 wt% solution (A2) of pale yellow transparent polyester phthalic acid. A part of the solution was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight of the obtained polymer (A2) was 10,000.

[Synthesis Example 3] Synthesis of Polyester Amidinic Acid Solution (A3)

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.

Thereafter, the reaction liquid was cooled to 25 ° C, and 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.

[Z/Y=8.0, (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 9,000.

[Synthesis Example 4] Synthesis of Polyester Amidinic Acid Solution (A4)

In a four-necked flask equipped with a stirrer, the following weights were loaded in order. Water-purified PGMEA, diethylene glycol methyl ethyl ether (hereinafter abbreviated as "EDM"), ODPA, SMA1000P, 1,4-butanediol, benzyl alcohol, stirred under a dry nitrogen stream at 120 ° C for 3 hours. .

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.

[Z/Y=2.0, (Y+Z)/X=1.0]

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 weight average molecular weight of the obtained polymer (A4) was 21,000.

Next, a mixture obtained by reacting a glycidyl (meth)acrylate and a bifunctional (meth) acrylate as essential raw material components is synthesized as follows. The epoxy group-containing polymer (Synthesis Example 5, Synthesis Example 6, Synthesis Example 7, Synthesis Example 8, and Synthesis Example 9).

[Synthesis Example 5] Synthesis of epoxy group-containing polymer solution (B1)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 420.00 g of MMP subjected to dehydration purification and glycidyl methacrylate (hereinafter abbreviated as "GMA") 162.00 g, 18.00 g of ethylene glycol dimethacrylate and 27.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were heated at a polymerization temperature of 110 ° C for 2 hours. Perform polymerization. A 30% by weight solution (B1) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,600 (in terms of polystyrene).

[Synthesis Example 6] Synthesis of epoxy group-containing polymer solution (B2)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 300.00 g of MMP subjected to dehydration purification, 180.00 g of GMA, and 20.00 g of 1,4-butanediol dimethacrylate were placed. 20.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. A 40% by weight solution (B2) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 12,000 (in terms of polystyrene).

[Synthesis Example 7] Synthesis of epoxy group-containing polymer solution (B3)

The 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet was charged with dehydrated and purified MMP 420.00 g, GMA 126.00. g, diethylene glycol dimethacrylate 18.00 g, tetrahydrofurfuryl methacrylate 36.00 g, 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator 27.00 g, the polymerization was carried out by heating at a polymerization temperature of 110 ° C for 2 hours. A 30% by weight solution (B3) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,500 (in terms of polystyrene).

[Synthesis Example 8] Synthesis of epoxy group-containing polymer solution (B4)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 420.00 g of MMP subjected to dehydration purification, 144.00 g of GMA, 27.00 g of diethylene glycol dimethacrylate, and methacryl were placed. 9.00 g of decyloxyorganopolyoxyalkylene (trade name; FM-0721, JNC Co., Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) 27.00 g as a polymerization initiator The polymerization was carried out by heating at a polymerization temperature of 110 ° C for 2 hours. A 30% by weight solution (B4) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 3,900 (in terms of polystyrene).

[Synthesis Example 9] Synthesis of epoxy group-containing polymer solution (B5)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 420.00 g of MMP subjected to dehydration purification, 126.00 g of GMA, 18.00 g of diethylene glycol dimethacrylate, and acrylic acid-2 were placed. 36.00 g of hydroxyethyl ester and 27.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator were heated at a polymerization temperature of 110 ° C for 2 hours to carry out polymerization. By cooling the reaction solution to A 30% by weight solution (B5) of the epoxy group-containing polymer was obtained at 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 4,500 (in terms of polystyrene).

[Comparative Synthesis Example 1] Synthesis of epoxy group-containing polymer (C1)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 300.00 g of MMP subjected to dehydration purification, 180.00 g of GMA, 20.00 g of methyl methacrylate, and 2 as a polymerization initiator were placed. 8.00 g of 2'-azobis(2,4-dimethylvaleronitrile) was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. A 40% by weight solution (C1) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 15,000 (in terms of polystyrene).

[Comparative Synthesis Example 2] Synthesis of epoxy group-containing polymer (C2)

In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 300.00 g of MMP subjected to dehydration purification, 180.00 g of GMA, and 20.00 g of 1,4-butanediol dimethacrylate were placed. 13.00 g of 2,2'-azobis(2,4-dimethylvaleronitrile) as a polymerization initiator was heated at a polymerization temperature of 90 ° C for 2 hours to carry out polymerization. A 40% by weight solution (C1) of the epoxy group-containing polymer was obtained by cooling the reaction liquid to 30 ° C or lower. A part of this solution was sampled, and the weight average molecular weight measured by GPC was 58,000 (in terms of polystyrene).

Next, polyester phthalic acid (A1, A2, A3, and A4) obtained in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4, Synthesis Example 5, Synthesis Example 6, Synthesis Example 7, and The epoxy group-containing polymerization obtained in Synthesis Example 8 and Synthesis Example 9 The materials (B1, B2, B3, B4, and B5), the comparative synthesis examples 1, the epoxy group-containing polymers (C1 and C2) obtained in Comparative Synthesis Example 2, the commercially available polyfunctional, and the weight average molecular weight of less than 3,000. The epoxy compound and the epoxy hardener were prepared as follows, and a thermosetting composition was prepared. A cured film was obtained from the thermosetting composition, and the cured film was evaluated (Reference Example 1 to Reference Example 8, Example 1 to Example 4, and Comparative Example 1 to Comparative Example 5).

[Reference Example 1]

A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100.0 g of the polyester phthalic acid solution (A1) obtained in Synthesis Example 1 was placed in the flask, and the epoxy group obtained in Synthesis Example 5 was contained. 175.0 g of polymer solution (B1), trimellitic anhydride (hereinafter abbreviated as "TMA") 6.0 g as an epoxy curing agent, 3-glycidoxypropyltrimethoxydecane 4.4 g as an additive, and Eddie Costa Wave (ADK STAB) AO-60 (trade name; ADEKA Co., Ltd.) 0.4 g, dehydrated and purified MMP 230.8 g and EDM 105.8 g as a solvent, and stirred at room temperature for 3 hr. It dissolves evenly. Next, 0.2 g of Megafac F-477 (trade name; Di Ai Sheng (DIC) Co., Ltd.) was charged, and the mixture was stirred at room temperature for 1 hour, and filtered with a membrane filter having a pore size of 0.2 μm to prepare a coating liquid. .

Next, the coating liquid was spin-coated on a glass substrate and a color filter substrate at 800 rpm for 10 seconds, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a coating film. Thereafter, the film was heated at 230 ° C for 30 minutes in an oven to cure the coating film to obtain a cured film having a film thickness of 1.5 μm.

Regarding the cured film obtained as described above, properties were evaluated regarding transparency, light resistance, flatness, heat resistance, and chemical resistance.

[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 97% or more was evaluated as "○", and the case where the transmittance was less than 97% was evaluated as "x".

[Evaluation method of light resistance]

For the glass substrate with a cured film after the transparency was evaluated in the [Evaluation Method for Transparency], an ultraviolet ozone cleaning device (trade name; PL2003N-12, light source; low-pressure mercury lamp, SEN special light source) was used. Co., Ltd.) UV treatment of 1J/cm ² (254nm conversion), after heating in an oven at 230 ° C for 30 minutes, using UV-visible near-infrared spectrophotometer (trade name; V-670, Japan Spec. Ltd.) The transmittance of light having a hardened film having a wavelength of 400 nm was measured. The case where the transmittance was 96% or more was evaluated as "○", and the case where the transmittance was less than 96% was evaluated as "x".

[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 by a step/surface roughness/fine shape measuring device (trade name; P-15, KLA TENCOR Co., Ltd.) . The case where the maximum value of the step difference between the R, G, and B elements including the black matrix (hereinafter abbreviated as "maximum step difference") is less than 0.3 μm is evaluated as "○", and the case where 0.3 μm or more is evaluated as "×. "." Moreover, The color filter substrate used is a pigment-dispersed color filter (hereinafter abbreviated as "CF") using a resin black matrix having a maximum step difference of about 0.5 μm.

[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 the step/surface roughness/fine shape measuring device (trade name; P-15, KLA TENCOR Co., Ltd.). 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

[Method for evaluating chemical resistance]

The obtained glass substrate with a cured film was immersed in a 5% by weight aqueous sodium hydroxide solution at 60 ° C for 10 minutes (hereinafter abbreviated as "NaOH treatment"), and contained 36% hydrochloric acid / 60% nitric acid. / Water = 40/20/40 mixture (weight ratio), immersion treatment at 50 ° C for 5 minutes (hereinafter abbreviated as "acid treatment"), in N-methyl-2-pyrrolidone, at 50 ° C The immersion treatment (hereinafter abbreviated as "NMP treatment") was carried out for 30 minutes, and then reheating was performed at 230 ° C for 1 hour. The residual film ratio after reheating and the transmittance after reheating were measured. The case where the residual film ratio after reheating was 90% or more and the transmittance at 400 nm after reheating was 95% or more was evaluated as "○". The residual film rate after reheating is less than 90% or the transmittance after reheating Less than 95% of the cases were evaluated as "X".

Remaining film ratio after reheating = (thickness after reheating / film thickness before reheating) × 100

[Reference Example 2 to Reference Example 8]

Each component was mixed and dissolved in the ratio (unit: g) shown in Table 1 according to the method of Reference Example 1, and the thermosetting 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; JNC Co., Ltd.), and AO-60 represents an antioxidant Edicos. ADB STAB AO-60 (trade name; ADEKA Co., Ltd.), F-477, F-556 and RS-72-K respectively represent the surfactant, Megafac F-477 , Megafac F-556, and Megafac RS-72-K (both trade names; Di Ai Sheng (DIC) Co., Ltd.).

[Example 1 to Example 4]

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

[Comparative Example 1 to Comparative Example 5]

According to the method of Reference Example 1, each component was mixed and dissolved in the ratio (unit: g) of Table 3 to obtain a thermosetting composition.

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

According to the results shown in Tables 5 and 6, the cured films of Examples 1 to 4 were excellent in light resistance and flatness, and balanced in all aspects of transparency, heat resistance, and chemical resistance. On the other hand, in Comparative Example 1 and Comparative Example 2, an epoxy group-containing polymer (the epoxy group-containing polymer was obtained by reacting glycidyl methacrylate and a monofunctional methacrylate) The cured film is excellent in light resistance, but the flatness is on the selected/falling line of the evaluation, and the heat resistance and chemical resistance are inferior. The use of the epoxy group-containing polymer of Comparative Example 3 (the epoxy group-containing polymer is obtained by reacting glycidyl methacrylate having a molecular weight of 50,000 or more and a bifunctional methacrylate) The flatness of the film is poor. Moreover, as for Comparative Example 4 and Comparative Example 5, the unused epoxy resin was used. As the base polymer, a cured film of an epoxy compound having a polyfunctional weight average molecular weight of less than 3,000 was used, and in Comparative Example 4, light resistance was poor, and in Comparative Example 5, heat resistance and chemical resistance were inferior. As described above, an epoxy group-containing polymer obtained by carrying out a reaction by using a glycidyl (meth)acrylate and a bifunctional (meth) acrylate as essential raw material components (weight average molecular weight; 1,000~) All features are met in the case of 50,000).

In addition, it is understood that each of the evaluation items of Reference Example 1 to Reference Example 8 in which the epoxy compound is not used as shown in Table 4 is "○", but some of the light resistance is inferior to the numerical value of the Example. A larger value than the embodiment is shown in the flatness.

[Industrial availability]

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

Claims (21)

A thermosetting composition comprising a polyester phthalic acid, an epoxy group-containing polymer, an epoxy compound, and an epoxy hardener, characterized in that the polyester proline is passed Obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components; the polyester phthalic acid is obtained by making X-mole of the tetracarboxylic dianhydride, Y-mole The polyamine compound of the diamine and Z mole is obtained by reacting at a ratio in which the relationship between the following formula (1) and formula (2) is satisfied, and has a structural unit and a formula represented by the following formula (3) ( 4) the structural unit represented; the epoxy group-containing polymer is obtained by reacting glycidyl (meth)acrylate and a bifunctional (meth) acrylate as essential raw material components, and the weight average molecular weight is 1,000 to 50,000; the epoxy compound contains 2 to 10 epoxy groups per molecule, and the weight average molecular weight is less than 3,000; and the epoxy group-containing content is 100 parts by weight with respect to the polyester phthalic acid The total amount of the polymer and the epoxy compound is from 20 parts by weight to 400 parts by weight, The epoxy hardener is 0.1 parts by weight to 60 parts by weight for the total amount of the epoxy group-containing polymer and the epoxy compound, and 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 removed from the diamine. A residue formed by -NH ₂ , and R ³ is a residue obtained by removing two -OH groups from the polyvalent hydroxy compound. The thermosetting composition according to claim 1, wherein the raw material component of the polyester phthalic acid further comprises a monohydroxy compound. The thermosetting 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- One or more kinds of ethyl-3-hydroxymethyloxetane. The thermosetting composition according to claim 1 or 2, wherein the raw material component of the polyester phthalic acid further comprises a styrene-maleic anhydride copolymer. The thermosetting 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 thermosetting composition as described in 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-butanetetracarboxylic dianhydride, and ethylene glycol bis(dehydrated benzotriene) One or more kinds of acid esters). The thermosetting composition according to claim 1 or 2, wherein the diamine is selected from the group consisting of 3,3'-diaminodiphenylphosphonium and bis[4-(3-amino) One or more kinds of phenoxy)phenyl]fluorene. The thermosetting 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. One or more kinds of 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate. The thermosetting composition according to claim 1 or 2, wherein the bifunctional (meth) acrylate is selected from the group consisting of ethylene glycol di(meth)acrylate and diethylene glycol (Meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,3-butylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, three One or more kinds of cyclodecane dimethanol di(meth)acrylate. The thermosetting composition according to claim 1 or 2, wherein the epoxy group-containing polymer is further comprising, in the raw material component, a glycidyl (meth)acrylate selected from the group consisting of It is obtained by reacting a radically polymerizable monomer other than the compound of the group consisting of the above-mentioned bifunctional (meth)acrylate. The thermosetting composition according to claim 10, wherein the glycidyl (meth)acrylate and the bifunctional (meth) acrylate are selected from the group consisting of The radical polymerizable monomer other than the compound of the group is selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and benzyl (meth)acrylate. , cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3- (meth) propylene methoxy propyl Triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, (meth) acryloxypropyl-tris-trimethyl decyloxy decane, (meth) propylene oxime Organopolyoxymethane, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, γ-butyrolactone (methyl) Acrylate, N-cyclohexylmaleimide, N-phenylmaleimide, 2,2,2-trifluoroethyl (meth)acrylate, (meth)acrylic acid, and 4-hydroxyl One or more kinds of phenyl vinyl ketone. The thermosetting composition according to claim 1 or 2, wherein the epoxy compound is selected from the group consisting of 3,4-epoxycyclohexanecarboxylic acid-3', 4'-epoxy ring Hexylmethyl ester, 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-[ a mixture of 4-(2,3-epoxypropoxyphenyl)-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol, and 2-[4-(2, 3-glycidoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane More than one type. The thermosetting composition according to the first or second aspect of the invention, wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole. The thermosetting 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 , 3,4-butane IV One or more kinds of carboxylic acid dianhydride; the diamine is 3,3'-diaminodiphenyl fluorene; the polyvalent hydroxy compound is 1,4-butanediol; and the epoxy group-containing polymer a copolymer having a weight average molecular weight of 1,000 to 50,000 obtained by reacting glycidyl methacrylate, diethylene glycol dimethacrylate, and tetrahydrofurfuryl methacrylate as a raw material component; The compound is 3,4-epoxycyclohexanecarboxylic acid-3',4'-epoxycyclohexylmethyl ester; the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride and 2-undecylimidazole; Further, one or more selected from the group consisting of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate are contained as a solvent. A cured film obtained by the thermosetting composition according to any one of claims 1 to 14. A color filter using the cured film as described in claim 15 as a protective film. A liquid crystal display element using the color filter of claim 16 of the patent application. A solid-state image pickup element using the color filter described in claim 16 of the patent application. A liquid crystal display element using the cured film as described in claim 15 as a transparent insulating film formed between the thin film transistor and the transparent electrode. A liquid crystal display element using the cured film as described in claim 15 as a transparent insulating film formed between the transparent electrode and the alignment film. A light-emitting diode illuminant using the cured film described in claim 15 as a protective film.