TW201725224A - Thermosetting compositions and use thereof - Google Patents

Abstract

To provide a cured film that is particularly excellent in light resistance and flatness and also excellent in heat resistance, chemical resistance such as solvent resistance, acid resistance and alkali resistance, water resistance, adhesion to underlying substrate such as glass, transparency, scratch resistance and coatability, and to provide a composition that gives this cured film. The thermosetting composition contains a polyester amide acid, an epoxy compound having a siloxane bond site, an epoxy compound having no siloxane bond site, and an epoxy curing agent, in which the polyester amide acid is obtained by reacting a tetracarboxylic acid dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material.

Description

Thermosetting composition and use thereof

The present invention relates to an insulating material usable 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 liquid crystal display element. A thermosetting composition such as a protective film, 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, various characteristics that can withstand various treatments in the manufacturing steps as described above are required. 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, coating property, and flatness are required. Light resistance and the like. 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 of 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 has a good flatness, but has insufficient heat resistance and is inferior in 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 Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. 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 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. It is excellent in scratch and coating property, and is particularly a cured film excellent in flatness and light resistance, and an electronic component including a composition for providing 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, an epoxy compound having a siloxane coupling site, an epoxy compound having no siloxane coupling site, and an epoxy curing agent, wherein the polyester phthalic acid is comprised of four It is obtained by a reaction of a compound of a carboxylic acid dianhydride, a diamine, and a polyvalent hydroxy compound. The present invention includes the following constitutions.

[1] A thermosetting composition comprising an epoxy phthalic acid, an epoxy compound having a siloxane coupling site, an epoxy compound having no siloxane coupling site, and an epoxy hardener. a composition obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components, and by using X-mole tetracarboxylic dianhydride, A polyester phthalic acid obtained by reacting a Y-mole diamine and a Z-mole polyvalent hydroxy compound at a ratio in which the relationship of the following formula (1) and formula (2) is established, 0.2 ≦Z/Y ≦ 8.0 ·· (1) 0.2≦(Y+Z)/X≦5.0 (2) Polyester phthalic acid has a structural unit represented by the following formula (3) and a structural unit represented by the formula (4) The total amount of the epoxy compound having a siloxane coupling site and the epoxy compound having no siloxane coupling site is 20 parts by weight to 400 parts by weight with respect to 100 parts by weight of the polyester phthalic acid; 100 parts by weight of the total epoxy compound, and 0 to 60 parts by weight of the epoxy curing agent; The proportion of the epoxy compound having a siloxane coupling site in the total amount of the epoxy compound is from 0.5% by weight to 70% by weight. (R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a polyvalent hydroxy compound residue).

[2] The thermosetting composition according to [1], wherein the raw material component of the polyester proline further comprises a monohydric alcohol.

[3] The thermosetting composition according to [2], wherein the monohydric alcohol 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 thermosetting composition according to any one of [1] to [3] wherein the raw material component of the polyester phthalic acid further comprises a styrene-maleic anhydride copolymer.

[5] The thermosetting composition according to any one of [1] to [4] wherein the polyester glutamic acid has a weight average molecular weight of 1,000 to 200,000.

[6] The thermosetting composition according to any one of [1] to [5] wherein the tetracarboxylic dianhydride is selected from 3,3',4,4'-diphenylphosphonium tetracarboxylic acid. Dihydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 2,2-[bis(3,4-dicarboxyphenyl)]hexafluoropropane dianhydride, 1,2, One or more of 3,4-butane tetracarboxylic dianhydride and ethylene glycol bis(hydrogen trimellitate).

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

[8] The thermosetting composition according to any one of [1] to [7] wherein the polyvalent hydroxy compound is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentyl One or more of a diol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and tris(2-hydroxyethyl) isocyanurate.

[9] The thermosetting composition according to any one of [1] to [8] wherein the epoxy compound having a siloxane coupling site is selected from the group consisting of compounds represented by the following formula (5) and At least one of the group of compounds represented by formula (6), (R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms or an organic group having an epoxy group, and R ^{7 is} independently hydrogen and an organic group having 1 to 26 carbon atoms; Or an organic group having an epoxy group; at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group, m is an integer of 2 or more, and R ⁴ or R ⁵ may be bonded to a bond. R ⁴ or R ⁵ bonded to different Si bonds to form a oxoxane ring, and R ⁶ and R ⁷ may also bond to form a siloxane chain) (R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen, an organic group having 1 to 26 carbon atoms or having an epoxy group; The organic group of the group, at least one of R ¹² and R ¹³ is an organic group having an epoxy group, n is an integer of 1 or more, and R ⁸ or R ⁹ may be bonded to R ⁸ and R ⁹ bonded to different Si. , R ¹⁰ , or R ^{11 is} bonded to form a oxoxane ring, and R ¹⁰ or R ¹¹ may also be bonded to R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ bonded to different Si. Hexane ring).

[10] The thermosetting composition according to any one of [1] to [9] wherein the epoxy compound having a siloxane coupling site is selected from the group consisting of 1,3-double [2-( 3,4-Epoxycyclohexyl)ethyl]tetramethyldioxane, 1,3-bis(3-glycidoxypropyl)tetramethyldioxane, 3-glycidoxy a copolymer obtained by reacting propyltrimethoxydecane as a raw material component, and by using 3-glycidoxypropyltrimethoxydecane, phenyltrimethoxydecane, and trimethylmethoxydecane as raw materials At least one of the group consisting of copolymers obtained by the reaction.

[11] The thermosetting composition according to any one of [1] to [9] wherein the epoxy curing agent is one or more selected from the group consisting of trimellitic anhydride, hexahydrotrimellitic anhydride, and 2-undecylimidazole.

[12] The thermosetting composition according to [1], wherein the tetracarboxylic dianhydride is 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride or 1,2,3,4 - butane tetracarboxylic dianhydride; diamine is 3,3'-diaminodiphenyl hydrazine; polyvalent hydroxy compound is 1,4-butanediol; epoxy compound having a siloxane coupling site is passed a copolymer having a weight average molecular weight of 1,000 to 200,000 obtained by reacting 3-glycidoxypropyltrimethoxydecane as a raw material component; an epoxy compound having no azide-bonding site is 2-[4 -(2,3-epoxypropoxy)phenyl]-2-[4-1,1-bis[4-([2,3-epoxypropoxy]phenyl)ethyl]benzene The epoxy hardener is trimellitic anhydride or 2-undecylimidazole; and further contains methyl 3-methoxypropionate or propylene glycol monomethyl ether acetate as a solvent.

[13] A cured film obtained by the thermosetting 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 liquid crystal display element using the color filter according to [14].

[16] A solid-state image pickup element using the color filter according to [14].

[17] A liquid crystal 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 liquid crystal 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 device using the cured film according to [13] as a transparent insulating film formed on a transparent electrode.

[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 thermosetting composition of the preferred embodiment of the present invention is particularly excellent in flatness and light resistance, and when used as a color filter protective film for 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.

1. Thermosetting composition The thermosetting composition of the present invention is an epoxy compound containing a polyester phthalic acid, a siloxane coupling site, an epoxy compound having no siloxane coupling site, and a ring. A composition of an oxygen hardener obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components. The thermosetting composition is characterized in that the composition has an epoxy compound having a siloxane coupling site and an epoxy having no siloxane coupling site with respect to 100 parts by weight of the polyester phthalic acid. The total amount of the compound is 20 parts by weight to 400 parts by weight, and the epoxy curing agent is 0 parts by weight to 60 parts by weight based on 100 parts by weight of the total of the epoxy compound, and the total amount of the epoxy compound is The proportion of the epoxy compound having a siloxane coupling site is from 0.5% by weight to 70% by weight. 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 phthalic acid 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- 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.

The synthesis of the polyester phthalic acid requires at least a solvent, and the solvent can be directly left to form a liquid or gel-like thermosetting composition in consideration of workability or the like, or the solvent can be removed for consideration. It is a solid composition such as handling property. Further, the synthesis of the polyester proline may optionally contain one or more compounds selected from the group consisting of a monohydroxy compound and a styrene-maleic anhydride copolymer, 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.

1-1-1. Tetracarboxylic dianhydride In the present invention, tetracarboxylic dianhydride is used as a material for obtaining polyester proline. 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. 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. Polyvalent hydroxy compound In the present invention, a polyvalent hydroxy compound is used as the material for obtaining the polyester phthalic acid. 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-pentanediol, 1,5-pentane Alcohol, 2,4-pentanediol, 1,2,5-pentanetriol, 1,2-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2,6- Hexatriol, 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, trimethylolpropane, pentaerythritol, dipentaerythritol, iso Tris(2-hydroxyethyl) cyanurate, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol S (bis(4-hydroxyphenyl)fluorene), 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 monoethyl ether, diethylene glycol monomethyl 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 a polyester phthalic acid formed by using these monohydroxy compounds, an epoxy compound having a siloxane coupling site, an epoxy compound having no siloxane coupling site, and an epoxy hardener. In the case of compatibility, or the coatability of the thermosetting composition on the color filter, 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 can be synthesized by adding a compound having three or more acid anhydride groups to the raw material. The improvement of the transparency of the polyester phthalic acid synthesized by adding a compound having three or more acid anhydride groups is expected, and therefore it is preferable. Examples of the compound having three or more acid anhydride groups include a styrene-maleic anhydride copolymer. The molar ratio of styrene/maleic anhydride 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 are trade names; Chuan crude oil 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. The amino decane compound having one amine group may be used as a raw material in the synthesis of the polyester valine acid, if necessary, without damaging the object of the present invention. Examples of such other raw materials include an aminodecane compound having one amine group. The aminodecane compound having an amine group is used to react with an acid anhydride group at the terminal of the polyester phthalic acid to introduce a decyl group at the terminal. The acid resistance of the resulting coating film can be improved by using a thermosetting composition of the present invention containing a polyester phthalic acid which is added by adding an amino decane compound having an amine group. Obtained by reaction. Further, when the reaction is carried out in the configuration of the monomer, a reaction may be carried out by adding both a monohydroxy compound and an aminodecane compound having one amine group.

Specific examples of the preferred aminodecane compound having an amine group used in the present invention include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, and 3-amino group. Propylmethyldimethoxydecane, 3-aminopropylmethyldiethoxydecane, 4-aminobutyltrimethoxydecane, 4-aminobutyltriethoxydecane, 4-amine Butylmethyldiethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, p-aminophenylmethyldimethoxydecane, p-aminophenylmethyl Diethoxydecane, m-aminophenyltrimethoxydecane, and m-aminophenylmethyldiethoxydecane. One or more of these amino decane compounds having one amine group can be used.

Among these amino group-containing decane compounds having an amine group, 3-aminopropyltriethoxydecane and p-aminophenyltrimethoxydecane having good acid resistance of the coating film are more preferable from acid resistance and compatibility. From a viewpoint, 3-aminopropyltriethoxydecane is particularly preferred.

It is preferable to contain 0 to 300 parts by weight of an aminodecane compound having one amine group 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. Solvents used in the synthesis reaction of polyester valine acid, and specific examples of the solvent used in the synthesis reaction for obtaining polyester proline are diethylene glycol dimethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxypropionic acid Ester, ethyl 3-ethoxypropionate, ethyl lactate, cyclohexanone, N-methyl-2-pyrrolidone, and N,N-dimethylacetamide. 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 valine acid The method for synthesizing polyester glutamic acid used in the present invention is to make tetracarboxylic dianhydride X-mole, diamine Y-mole in the solvent. And a polyhydroxy compound Z molar reaction. 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≦ is more preferable. Z/Y≦5.0. 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 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.

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 and 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.

When the amine decane compound having one amine group is reacted, after the reaction of the tetracarboxylic dianhydride with the diamine and the polyvalent hydroxy compound is completed, the reaction liquid is cooled to 40 ° C or lower, and then an amine is added. The amino group-based decane compound is preferably reacted at 10 to 40 ° C for 0.1 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. Epoxy Compound The epoxy compound used in the present invention may be an epoxy compound having a siloxane coupling site and an epoxy compound having no siloxane coupling site. It is preferable that an epoxy compound having a siloxane coupling site is in the epoxy compound from the viewpoint of exhibiting the properties of the epoxy compound having no siloxane coupling site to be described later without impairing the effects of the present invention. The ratio in the total amount is from 0.5% by weight to 70% by weight.

1-2-1. Epoxy compound having a siloxane coupling site The epoxy compound having a siloxane coupling site used in the present invention is as long as the phase forming the other component of the thermosetting composition of the present invention. There is no particular limitation on the solubility. The epoxy compound having a siloxane coupling site is preferably at least one selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the formula (6).

In the formula (5), R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and R ^{7 is} independently hydrogen and carbon, respectively. An organic group having 1 to 26 or an organic group having an epoxy group, and at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group. m is an integer of 2 or more, and R ⁴ or R ⁵ may be bonded to R ⁴ or R ⁵ bonded to a different Si to form a oxoxane ring, and R ⁶ and R ⁷ may be bonded to form a ring. A siloxane chain.

The organic group having 1 to 26 carbon atoms of R ⁴ , R ⁵ and R ⁶ is a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkyl group containing a cyclic alkyl group, an aromatic ring, and an aromatic ring. Any of the methylene groups (CH ₂ ) of these groups may be substituted by a group containing O, NH, N or a group containing Si, and any hydrogen of these groups may be substituted by fluorine.

Specific examples of the linear alkyl group and the branched alkyl group are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a t-amyl group, a hexyl group, and 2,3. - dimethylbutan-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

Specific examples of the cyclic alkyl group and the alkyl group containing a cyclic alkyl group are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a bicyclo[2.2.1]heptane-2- Base, bicyclo[2.2.1]hept-5-en-2-yl, 2-cyclohexylethyl, 2-(cyclohex-3-en-1-yl)ethyl, 2-cycloheptylethyl, 2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl, 3-cyclohexylpropyl, 4-(tert-butyl)cyclohexyl, and adamantyl.

Specific examples of the aromatic ring and the group containing the aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutyl Phenyl, 2,6-diethylphenyl, naphthalen-2-yl, 1,1'-biphenyl, 4'-(tert-butyl)-[1,1'-biphenyl]-4- , 2,4,6-triisopropylphenyl, 4'-heptyl-[1,1'-biphenyl]-4-yl, 12-((2-benzylidenebenzyl) )oxy)dodecyl, and fluoren-9-yl.

Specific examples of the group in which any methylene group (CH ₂ ) is substituted by a group containing O, N or Si are ethoxymethyl group, 3-methoxy-3-oxopropyl group, 3-(( 2-methoxyethoxy)propyl, 2,5,8,11-tetraoxatetradecane-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-Dimethoxyundecyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran 4-yl, 3-((tetrahydrofuran-3-yl)methoxy)propyl, 10-(1,3-dioxolan-2-yl)indolyl, 10-(1,3- Dioxan-2-yl)indenyl, morpholinyl, 4-methoxy-3,5-dimethylbenzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-carboxyl Ethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethyldecyl, (trimethyldecyl)methyl, 3-(trimethyldecyl)propyl, 2- (2,4,4,6,6,8,8-heptamethyl-1,3,5,7-tetraoxa-2,4,6,8-tetradecyloctane-2-yl) , 2-(dimethyl(phenyl)decyl)ethyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy, butoxy , tert-butoxy, sec-butoxy, isobutoxy, tert-amyloxy , hexyloxy, 2-ethylbutoxy, (3-methylpentyl)oxy, (2-methylhexane-2-yl)oxy, octyloxy, (2-ethylhexyl) Oxyl, decyloxy, 2-methoxyethoxy, 2-ethoxyethoxy, (1-methoxypropan-2-yl)oxy, 2-(2-methoxy Ethoxy)ethoxy, 2-butoxyethoxy, (3-ethylhexyl)oxy, dodecyloxy, tridecyloxy, hexadecyloxy, Octadecyloxy, stearyloxy, (butane-2-ylidene)oxy, (diethylamino)oxy, cyclohexyloxy, cyclooctyloxy, double Ring [2.2.1] heptane-2-yloxy, cyclodecyloxy, (2-isopropyl-5-methylcyclohexyl)oxy, (5-methyl-2-(propan-1) -alken-2-yl)cyclohexyloxy, (octahydro-1H-4,7-methylindole-5-yl)oxy, phenoxy, p-tolyloxy, m-tolyloxy, O-tolyloxy, o-carboxyphenoxy, benzyloxy, phenethyloxy, 3-phenylpropoxy, cinnamyloxy, 1-phenyl-(2-ethoxy-2-oxo Ethoxy), (2-methyl-1-oxo-1-phenylpropan-2-yl)oxy, 2-ethoxy-2-oxo-1-(o-tolyl)ethoxy base 2-ethoxy-1-(2-methoxyphenyl)-2-oxoethoxy, (4-ethoxy-4-oxo-1-phenylbut-2-ene-1- Alkyloxy, (1-benzylidenecyclohexyl)oxy, and 2-hydroxyethoxy.

Specific examples of the group in which any hydrogen is substituted by fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-nonfluorene. -4,4-bis(trifluoromethyl)octyl, 11-(perfluorophenoxy)undecyl, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl , 3-phenoxybenzyl, 4'-methoxy-[1,1'-biphenyl]-4-yl, 4-(octyloxy)phenyl, fluoromethoxy, difluoromethyl Oxyl, 2,2,2-trifluoroethoxy, 2,2,2-trifluoroacetoxy, 2,2,3,3-tetrafluoropropoxy, 2,2,3,3, 3-pentafluoropropoxy, (1,1,1,3,3,3-hexafluoropropan-2-yl)oxy, and perfluorophenoxy.

Among the above-mentioned groups, from the viewpoint of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film, a preferred group is a methyl group, an ethyl group, a propyl group or an isopropyl group. Butyl, isobutyl, tert-butyl, pentyl, tert-amyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl, phenyl Base, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, ethoxymethyl, 3-methoxy-3-oxopropyl, 3-(2-methoxyethoxy)propyl, 4-methoxy-3,5-dimethylbenzyl, trimethyldecyl, (Trimethyldecyl)methyl, 3-(trimethyldecyl)propyl, methoxy, ethoxy, propoxy, isopropoxy, prop-1-en-2-yloxy , butoxy, tert-butoxy, sec-butoxy, isobutoxy, tert-amyloxy, hexyloxy, 2-ethylbutoxy, cyclohexyloxy, cyclooctyloxy, benzene More preferred are oxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, benzyloxy, and 3-phenylpropoxy. Is methyl, ethyl, propyl, phenyl, benzyl, ethoxymethyl, trimethyldecyl, (trimethyldecyl)methyl, methoxy, ethoxy, and propoxy base.

The organic group having 1 to 26 carbon atoms in R ⁷ is also a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkyl group containing a cyclic alkyl group, an aromatic ring, a group containing an aromatic ring, and the like. Any methylene group (CH ₂ ) may be substituted by a group containing O, NH, N or a group containing Si, and any hydrogen of these groups may be substituted by fluorine, but since R ^{7 is} bonded to O, Specific examples are limited as compared with R ⁴ , R ⁵ and R ⁶ .

Specific examples of the linear alkyl group and the branched alkyl group are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a t-amyl group, a hexyl group, and 2,3. - dimethylbutan-2-yl, octyl, 6-methylheptyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl.

Specific examples of the cyclic alkyl group and the alkyl group containing a cyclic alkyl group are a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a bicyclo[2.2.1]heptane-2- Base, bicyclo[2.2.1]hept-5-en-2-yl, 2-cyclohexylethyl, 2-(cyclohex-3-en-1-yl)ethyl, 2-cycloheptylethyl, 2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl, 3-cyclohexylpropyl, 4-(tert-butyl)cyclohexyl, and adamantyl.

Specific examples of the aromatic ring and the group containing the aromatic ring are phenyl, benzyl, phenethyl, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutyl Phenyl, 2,6-diethylphenyl, naphthalen-2-yl, 1,1'-biphenyl, 4'-(tert-butyl)-[1,1'-biphenyl]-4- , 2,4,6-triisopropylphenyl, 4'-heptyl-[1,1'-biphenyl]-4-yl, 12-((2-benzylidenebenzyl) )oxy)dodecyl, and fluoren-9-yl.

Specific examples of the group in which any methylene group (CH ₂ ) is substituted by a group containing O, N or Si are ethoxymethyl group, 3-methoxy-3-oxopropyl group, 3-(( 2-methoxyethoxy)propyl, 2,5,8,11-tetraoxatetradecane-14-yl, 2,5,8,11-tetraoxaheptadecan-17-yl, 11,11-Dimethoxyundecyl, 2-(dimethylamino)ethyl, 2-(diethylamino)ethyl, tetrahydrofuran-3-yl, tetrahydro-2H-pyran 4-yl, 3-((tetrahydrofuran-3-yl)methoxy)propyl, 10-(1,3-dioxolan-2-yl)indolyl, 10-(1,3- Dioxan-2-yl)indenyl, morpholinyl, 4-methoxy-3,5-dimethylbenzyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1-carboxyl Ethyl, 4-hydroxybutyl, 4-hydroxy-3-oxobutyl, trimethyldecyl, (trimethyldecyl)methyl, 3-(trimethyldecyl)propyl, 2- (2,4,4,6,6,8,8-heptamethyl-1,3,5,7-tetraoxa-2,4,6,8-tetradecyloctane-2-yl) And 2-(dimethyl(phenyl)decyl)ethyl.

Specific examples of the group in which any hydrogen is substituted by fluorine are 3,3,3-trifluoropropyl, perfluorooctyl, 5,5,6,6,7,7,8,8,8-nonfluorene. -4,4-bis(trifluoromethyl)octyl, 11-(perfluorophenoxy)undecyl, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl 3-phenoxybenzyl, 4'-methoxy-[1,1'-biphenyl]-4-yl, and 4-(octyloxy)phenyl.

Among the above-mentioned groups, from the viewpoint of excellent compatibility in the composition of the compound and good transparency and flatness of the formed cured film, a preferred group is a methyl group, an ethyl group, a propyl group or an isopropyl group. Butyl, isobutyl, tert-butyl, pentyl, tert-amyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, phenyl, benzyl, phenyl Base, 4-isopropylphenyl, mesityl, 3,5-diethylphenyl, 4-isobutylphenyl, 2,6-diethylphenyl, ethoxymethyl, 3-methoxy-3-oxopropyl, 3-(2-methoxyethoxy)propyl, 4-methoxy-3,5-dimethylbenzyl, trimethyldecyl, (Trimethyldecyl)methyl, and 3-(trimethyldecyl)propyl, more preferred are methyl, ethyl, propyl, phenyl, benzyl, ethoxymethyl, Trimethyldecyl, and (trimethyldecyl)methyl.

The organic group having an epoxy group of R ⁴ , R ⁵ , R ⁶ and R ^{7 is} specifically an oxiran-2-ylmethyl group, a 2-(oxiranoyl-2-yl)ethyl group, 4- (oxirane-2-yl)butyl, 3-(oxirano-2-ylmethoxy)propyl, 7-oxabicyclo[4.1.0]heptan-3-yl, 2- (7-oxabicyclo[4.1.0]heptan-2-yl)ethyl, dimethyl(4-(oxirano-2-ylmethoxy)butyl)decyl, 3-(7 -oxabicyclo[4.1.0]heptan-3-yl)propyl, and 8-(oxacyclopropan-2-yl)octyl.

Among the above, from the viewpoint of good transparency and heat resistance of the formed cured film, preferred groups are oxiran-2-ylmethyl and 2-(oxiran-2-yl) , 4-(oxirano-2-yl)butyl, 3-(oxirano-2-ylmethoxy)propyl, 7-oxabicyclo[4.1.0]heptane-3- And 2-(7-oxabicyclo[4.1.0]heptan-2-yl)ethyl, more preferred are oxiran-2-ylmethyl, 2-(oxirane- 2-yl)ethyl, 4-(oxetan-2-yl)butyl, 3-(oxirano-2-ylmethoxy)propyl.

In the formula (6), R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen and have a carbon number of 1 to 26. An organic group or an organic group having an epoxy group, at least one of R ¹² and R ¹³ is an organic group having an epoxy group. n is an integer of 1 or more, and R ⁸ or R ⁹ may be bonded to R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ bonded to a different Si to form a oxene oxide ring, and R ¹⁰ or R ¹¹ may also be bonded to R ⁸ , R ⁹ , R ¹⁰ , or R ¹¹ bonded to a different Si to form a oxane ring.

The organic group having 1 to 26 carbon atoms and the organic group having an epoxy group in R ⁸ to R ¹³ may be the same as those exemplified in R ⁴ , R ⁵ and R ⁶ in the above formula (5). The base, more preferred groups are also the same.

The weight average molecular weight of the epoxy compound having a siloxane coupling site is preferably from 200 to 10,000, and more preferably from 200 to 5,000. If it is in these ranges, the flatness becomes good. Therefore, the value of m in the formula (5) is preferably 2 to 50, more preferably 2 to 25. The value of n in the formula (6) is preferably 1 to 74, and more preferably 1 to 36.

The ratio of the epoxy compound having a siloxane coupling site in the total amount of the epoxy compound having no siloxane coupling site and the epoxy compound having a siloxane coupling site is 0.5% by weight to 70% by weight. It is preferably from 1% by weight to 50% by weight. If it is in these ranges, the balance of flatness, transparency, heat resistance, and tackiness becomes good.

A specific example of the epoxy compound having a siloxane coupling site is an organic hydrazine compound having an epoxy group and capable of generating a decane bond by further condensation; having an epoxy group and generating a decane by condensation a copolymer of one or more organic ruthenium compounds having a bond; or one or more organic ruthenium compounds having the epoxy group and capable of generating a decane bond by condensation, and having no siloxane bond by condensation A copolymer of an epoxy group organic hydrazine compound. If it is a commercially available product, 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldioxane (trade name; limited edition of the company) Company (made by Gelest Technologies Incorporated), TSL9906 (trade name; Momentive Performance Material (manufactured)), CoatOsil MP-200 (trade name; Momentive Advanced Materials) ))), Conpoceran SQ506 (trade name; manufactured by Arakawa Chemical Co., Ltd.), ES-1023 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.).

1-2-2. Epoxy compound having no siloxane coupling site The epoxy compound having no siloxane coupling site used in the present invention is only required to form other components of the thermosetting composition of the present invention. The compatibility is not particularly limited, and examples thereof include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and a bisphenol A. a novolac type epoxy resin, an aliphatic polyglycidyl ether compound, or a cyclic aliphatic epoxy resin, a polymer of a monomer having an epoxy group, and a copolymer of a monomer having an epoxy group and another monomer Wait.

Examples of the glycidyl ether type epoxy resin include: TECHMORE VG3101L (trade name; Printec Co., Ltd.), EHPE-3150 (trade name; Daicel Co., Ltd.), EPPN- 501H, EPPN-502H (both trade names; Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; Mitsubishi Chemical Corporation). Examples of the glycidyl ester type epoxy resin include: Denacol EX-721 (trade name; Nagase ChemteX Co., Ltd.), 1,2-cyclohexanedicarboxylic acid diglycidyl ester (trade name; manufactured by Tokyo Chemical Industry Co., Ltd.), phenol novolac type epoxy resin: EPPN-201 (trade name; Nippon Kayaku Co., Ltd.), JER 152, JER 154 (all are trade names; Mitsubishi Chemical Co., Ltd.), etc. Examples of the cresol novolac type epoxy resin include EOCN-102S, EOCN-103S, EOCN-104S, and EOCN-1020 (both of which are trade names; Nippon Kayaku Co., Ltd.). Examples of the bisphenol A novolac type epoxy resin include JER 157S65 and JER 157S70 (all trade names; Mitsubishi Chemical Corporation). Examples of the cyclic aliphatic epoxy resin include Celloxide 2021P and Celloxide 3000 (all trade names; Daicel Co., Ltd.).

1-3. Epoxy Curing Agent In the thermosetting composition of the present invention, an epoxy curing agent can be 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, hexahydrotrimellitic anhydride, etc.) An aromatic polycarboxylic acid anhydride (for example, phthalic anhydride, trimellitic anhydride, etc.) or a styrene-maleic anhydride copolymer. 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 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 preferable.

1-4. Ratio of Polyester Proline, Epoxy Compound, and Epoxy Hardener to 100 Weight Parts of Polyester Proline in the Thermosetting Composition of the Present Invention, and Ratio of Total Epoxy Compound It is 20 parts by weight to 400 parts by weight. When the ratio of the total amount of 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 compound is preferably in the range of 50 parts by weight to 300 parts by weight.

In the thermosetting composition of the present invention, when an epoxy curing agent is used, the ratio of the epoxy curing agent is from 0.1 part by weight to 60 parts by weight based on 100 parts by weight of the epoxy compound. 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 to 1.5 times the epoxy group. Add in the same way. At this time, the carboxylic anhydride group is calculated by divalent. 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, which is more preferable.

1-5. Other components Various additives may be added to the thermosetting composition of the present invention to improve coating uniformity and adhesion. 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.

1-5-1. Solvent A solvent may be added to the thermosetting composition of the present invention. The solvent to be added arbitrarily in the thermosetting composition of the present invention is preferably a solvent which can dissolve the polyester phthalic acid, the epoxy compound, the epoxy curing agent or the like. Specific examples of the solvent are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, acetone, 2-butanone, ethyl acetate, acetic acid Butyl ester, propyl acetate, butyl propionate, ethyl lactate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetate Ester, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, 3-methoxypropionic acid Ethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2 -ethyl methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-hydroxy-2-methylpropionic acid Ester, ethyl 2-hydroxy-2-methylpropanoate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, Ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4 -methyl-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, ethylene glycol monomethyl ether, ethylene glycol single 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, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol single Butyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, acetonitrile, dioxane, toluene, two Toluene, γ-butyrolactone, or N,N-dimethylacetamide, and cyclohexanone. The solvent may be one of these solvents, or a mixture of two or more of these solvents.

1-5-2. Surfactant In the thermosetting composition of the present invention, a surfactant may 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 above) For 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, Meijia Method (Megafac) F-553, Megafac F-554, Meijiafa 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 Ai Sheng ( DIC), TEGO Twin 4000, TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, Digograd TEGO Glide 440, TEGO Glide 450, TEGO Rad 2200N, TEGO Rad 2250N (all of which are trade names, Evonik Degussa, Japan) (Evonik-Degussa Japan) Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl Sulfonate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene Octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearin Ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan hard Fatty acid ester, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, poly Oxyethylene sorbitan oleate, polyoxyethylene naphthyl ether, alkyl benzene 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 650A, Megafac F-477, Megafac F-556, Megafac RS-72-k, TEGO Twin 4000, fluoroalkylbenzenesulfonate, fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, fluoroalkyl sulfonate, fluoroalkyl trimethyl ammonium salt, and fluoroalkyl amine sulfonate At least one of them is preferable because the coating uniformity of the thermosetting composition is high.

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.

1-5-3. Adhesion improving agent 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 Sarah-Ace) ) S530; trade name; JNC Co., Ltd.), 3-mercaptopropyltrimethoxydecane (for example, Sila-Ace S810; trade name; JNC Co., Ltd.) and other decane coupling agents, 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-glycidoxypropyltriethoxydecane 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 thermosetting composition. On the other hand, it is preferably 0.01% by weight or more.

1-5-4. Antioxidant 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, ADIK STAB AO-50, ADIK STAB AO-60, Ai Kos Tabor (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.

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.

1-5-7. 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.

1-6. Storage of the 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. Cured film obtained from a thermosetting composition The thermosetting composition of the present invention can be obtained by: a polyester phthalic acid, an epoxy compound having a siloxane coupling site, and no argon The epoxy compound and the epoxy hardener at the alkene bond site are mixed, and depending on the target characteristics, a solvent, a coupling agent, a surfactant, and other additives are optionally added as needed, and these compounds are uniformly mixed and dissolved.

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. 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, 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 proline is dehydrated and cyclized to form a quinone bond, and 2) the carboxylic acid of the polyester phthalic acid is reacted with the epoxy compound. Since the polymer compound is highly polymerized and 3) the epoxy compound is hardened and polymerized, 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, 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 glutamic acid solution (A1) In a four-necked flask equipped with a stirrer, methyl 3-methoxymethyl 3-methoxypropionate (methyl 3-methoxy) was charged and purified under the following weight. Propionate, hereinafter abbreviated as "MMP"), 3,3',4,4'-diphenylether tetracarboxylic dianhydride (hereinafter referred to as "ODPA") ), 1,4-butanediol, and benzyl alcohol were stirred at 130 ° C for 3 hours under a stream of dry nitrogen. MMP 446.96 g ODPA 183.20 g 1,4-butanediol 31.93 g benzyl alcohol 25.54 g Thereafter, the reaction solution was cooled to 25 ° C, and 3,3'-diamino diphenyl sulfone was added in the following weight. Hereinafter, abbreviated as "DDS") and MMP, the mixture was stirred at 20 ° C to 30 ° C for 2 hours, and then 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 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 (propylene glycol monomethyl ether) which was subjected to dehydration purification was sequentially placed in the following weight. Acetate, hereinafter abbreviated as "PGMEA"), 1,2,3,4-butanetetracarboxylic dianhydride (hereinafter abbreviated as "BT-100"), SMA1000P (trade name; styrene-maleic anhydride copolymer, Chuan Crude Oil Co., Ltd.), 1,4-butanediol, and benzyl alcohol were stirred at 125 ° C for 3 hours under a stream of dry nitrogen. PGMEA 324.00 g BT-100 30.64 g SMA1000P 145.88 g 1,4-butanediol 9.29 g benzyl alcohol 44.59 g Thereafter, the reaction solution was cooled to 25 ° C and charged with DDS and PGMEA at the following weights, at 20 ° C to 30 ° C After stirring for 2 hours, the mixture was stirred at 125 ° C for 2 hours. DDS 9.60 g PGMEA 36.00 g [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) In a four-necked flask equipped with a stirrer, PGMEA, BT-100, SMA1000P, and 1,4- Butanediol and benzyl alcohol were stirred at 125 ° C for 3 hours under a stream of dry nitrogen. PGMEA 324.00 g BT-100 30.04 g SMA1000P 143.05 g 1,4-butanediol 9.11 g benzyl alcohol 54.66 g Thereafter, the reaction solution was cooled to 25 ° C and charged with DDS and PGMEA at a weight of 20 ° C to 30 ° C at the following weight: After stirring for 2 hours, the mixture was stirred at 125 ° C for 2 hours. DDS 3.14 g PGMEA 36.00 g [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, PGMEA and diethylene glycol methyl ethyl ether which were subjected to dehydration purification were sequentially placed under the following weights ( Diethylene glycol methyl ethyl ether (hereinafter abbreviated as "EDM"), ODPA, SMA1000P, 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 solution was cooled to 25 ° C, and DDS and MMP were added at a weight of 20 ° C to 30 ° C with the following weight: After stirring for 2 hours, the mixture was 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 (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 copolymer obtained by reacting one or more organic hydrazine compounds having an epoxy group and capable of generating a decane bond by condensation as a raw material component is synthesized as follows, as a site having a siloxane coupling site. Epoxy compound (Synthesis Example 5 and Synthesis Example 6).

[Synthesis Example 5] Synthesis of epoxy compound (S1) having a siloxane coupling site In a 1000 ml four-necked flask, 109.24 g of toluene purified by dehydration, 21.62 g of purified water, and 25% by weight were charged. The concentration of tetramethylammonium hydroxide (hereinafter abbreviated as "TMAH") was 2.92 g, and stirring was started. Further, in a 300 ml cylindrical dropping funnel, 53.78 g of toluene purified by dehydration and purified, Sila-Ace S510 (trade name; manufactured by JNC), and hereinafter referred to as "S510" 94.54 g of the solution was added as a dropping liquid, and the total amount was poured into the 1000 ml four-necked flask filled with the raw material over 1 hour, and then stirred for 2 hours to carry out condensation. The reaction liquid was subjected to liquid separation using purified water, and toluene was distilled off from the obtained organic layer using a rotary evaporator, whereby an epoxy compound (S1) having a siloxane coupling site was obtained. The weight average molecular weight of this solution measured by GPC was 3,200 (in terms of polystyrene).

[Synthesis Example 6] Synthesis of epoxy compound (S2) having a siloxane coupling site In a 1000 ml four-necked flask, 137.64 g of toluene purified by dehydration, 32.44 g of purified water, and 25% by weight were charged. The concentration of tetramethylammonium hydroxide aqueous solution (hereinafter abbreviated as "TMAH") was 4.38 g, and stirring was started. Further, in a 300 ml cylindrical dropping funnel, 67.76 g of toluene purified by dehydration, 28.37 g of Sila-Ace S510, 59.48 g of phenyltrimethoxydecane, and trimethyl group were charged. 31.26 g of methoxy decane was added as a dropping liquid, and the total amount was poured into the 1000 ml four-necked flask in which the raw material was placed over 1 hour, and then stirred for 2 hours to carry out condensation. The reaction liquid was subjected to liquid separation using purified water, and toluene was distilled off from the obtained organic layer using a rotary evaporator, whereby an epoxy compound (S2) having a siloxane coupling site was obtained. The weight average molecular weight of this solution measured by GPC was 1,900 (in terms of polystyrene).

Next, a copolymer obtained by reacting a monomer having an epoxy group and another monomer copolymerized with the monomer as a raw material component as a raw material having no siloxane coupling site is synthesized as follows. Epoxy compound (Synthesis Example 7 and Synthesis Example 8).

[Synthesis Example 7] Synthesis of epoxy compound solution (E1) having no siloxane coupling site In a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, it was charged and dehydrated. Purified MMP 300.00 g, glycidyl methacrylate (hereinafter abbreviated as "GMA") 160.00 g, butyl methacrylate (hereinafter abbreviated as "BMA") 40.00 g, as a polymerization initiator The 2,2'-azobis(2,4-dimethylvaleronitrile) 8.00 g was polymerized by heating at a polymerization temperature of 90 ° C for 2 hours. An epoxy compound 40% by weight solution (E1) having no siloxane coupling site was obtained by cooling the reaction liquid to 30 ° C or lower. The weight average molecular weight of this solution measured by GPC was 78,000 (in terms of polystyrene).

[Synthesis Example 8] Synthesis of epoxy compound solution (E2) having no azide-bonding site was carried out in a 1000 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet. Purified MMP 420.00 g, glycidyl methacrylate 162.00 g, diethylene glycol dimethacrylate 18.00 g, 2,2'-azobis(2,4-dimethylpentane) as polymerization initiator The nitrile was 27.00 g, and polymerization was carried out by heating at a polymerization temperature of 110 ° C for 2 hours. An epoxy compound 30% by weight solution (E2) having no oxyalkylene bond site was obtained by cooling the reaction liquid to 30 ° C or lower. The weight average molecular weight of this solution measured by GPC was 3,600 (in terms of polystyrene).

Next, the polyester proline acids (A1, A2, A3, and A4) obtained in Synthesis Example 1, Synthesis Example 2, Synthesis Example 3, and Synthesis Example 4 were used; the obtained in Synthesis Example 5 and Synthesis Example 6 were obtained. An epoxy compound at a site of a siloxane coupling; an epoxy compound having no siloxane coupling site obtained in Synthesis Example 7 and Synthesis Example 8; a commercially available epoxy resin (having a siloxane coupling site) An epoxy compound or an epoxy compound having no siloxane coupling site; and an epoxy hardener, a thermosetting composition is prepared as follows. A cured film was obtained from the thermosetting composition, and the cured film was evaluated (Examples 1 to 11 and Comparative Examples 1 to 6).

[Example 1] A 500 ml separable flask equipped with a stirring blade was purged with nitrogen, and 100.00 g of the polyester phthalic acid solution (A1) obtained in Synthesis Example 1 was placed in the flask as a crucible. CoatOsil MP-200 (hereinafter abbreviated as "S3") 1.50 g of an epoxy compound of an oxyalkylene bond site, and TECHMORE as an epoxy compound having no azide bond site. ) VG3101L (trade name; Printec (share), hereinafter abbreviated as "E3") 58.50 g, trimellitic anhydride (hereinafter abbreviated as "TMA") 6.00 g as an epoxy hardener, Addicus as an additive ADB STAB AO-60 (trade name; manufactured by Adeco (ADEKA) Co., Ltd.) 0.48 g, dehydrated and purified MMP 367.38 g and EDM 109.34 g as a solvent, at room temperature for 3 hours Stir and dissolve evenly. Next, 0.17 g of Megafac F-556 (trade name; manufactured by Diane Health Co., Ltd.) was placed, stirred at room temperature for 1 hour, and filtered by 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 1.0 μm.

Regarding the cured film obtained in the above manner, properties were evaluated regarding transparency, light resistance, flatness, and heat resistance.

[Evaluation method of transparency] In the obtained glass substrate with a cured film, the wavelength of only the cured film was measured by an ultraviolet-visible near-infrared spectrophotometer (trade name; V-670, manufactured by JASCO Corporation). Transmittance of light under nm. 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".

[Method for Evaluating Light Resistance] A glass substrate with a cured film after evaluation of transparency in the above [Evaluation Method for Transparency] was subjected to an ultraviolet ozone cleaning device (trade name; PL2003N-12, light source; Low-pressure mercury lamp and SEN special light source (manufactured by SEN) are subjected to ultraviolet ozone treatment at 1 J/cm ² (254 nm conversion), and heated in an oven at 230 ° C for 30 minutes, followed by UV-visible infrared spectrophotometer (trade name) V-670, manufactured by Japan Spectrophotometer) The transmittance of light having a wavelength of 400 nm only for the cured film was measured. 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".

[Evaluation method of flatness] 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 step of the surface of the cured film. 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 0.25 μm is evaluated as "○", and the case where 0.25 μm or more is evaluated as "×" . Further, the color filter substrate used was a pigment dispersion 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 heated at 230 ° C for 1 hour, the film thickness before heating and the film thickness after heating were measured, and the residual film was calculated by the following calculation formula. rate. 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 96% or more was evaluated as "○", and the case where the residual film ratio after heating was less than 96% was evaluated as "x". Residual film rate = (film thickness after heating / film thickness before heating) × 100

[Evaluation Method of Viscosity] The coating liquid was spin-coated on a glass 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 presence or absence of a tuck is determined by palpation. When the pre-baked coating film was touched, the case where the shape of the film was not visually changed was evaluated as "○", and the case where the shape was changed was evaluated as "x".

[Examples 2 to 11] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 1-1 and Table 1-2 to obtain a thermosetting composition. Further, with respect to the abbreviations of the respective compounds in the table, S4 represents 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetra which is an epoxy compound having a siloxane coupling site. Methyldioxane (trade name; manufactured by Gelest Technologies Incorporated). S510 of the additive column indicates the adhesion improving agent Sila-Ace S510 (trade name; JNC Co., Ltd.), and AO-60 indicates the antioxidant AID STAB (AOK STAB) AO-60 (trade name) ; ADEKA (manufactured by ADEKA), F-556 represents the surfactant Megafac F-556 (trade name; manufactured by Di Love (DIC)).

[Comparative Example 1 to Comparative Example 6] According to the method of Example 1, each component was mixed and dissolved in the ratio (unit: g) described in Table 2 to obtain a thermosetting composition.

In addition, the evaluation results of the cured films of Examples 1 to 11 are collectively shown in Table 1-1 and Table 1-2, and the evaluation results of the cured films of Comparative Examples 1 to 6 are collectively shown in Table 2. .

Table 1-1

Table 1-2

Table 2

According to the results shown in Table 1, it is understood that the cured films of the epoxy compounds having the azide-bonding sites in Examples 1 to 11 are excellent in flatness, and are excellent in all aspects of transparency, light resistance, and heat resistance. Get balanced.

On the other hand, the cured films using only the epoxy compound in Comparative Example 1 and Comparative Example 5 and Comparative Example 6 were excellent in transparency and heat resistance, but were inferior in flatness. In the case where E3 is used for the epoxy compound in Comparative Example 2, and the epoxy compound having a decane-bonding site is used in an amount less than the preferred range, it is excellent in transparency, light resistance, and heat resistance, but is flat. Poor results. On the other hand, in the case of using the epoxy compound having a siloxane coupling site in an amount of more than the preferred range in Comparative Example 3 and Comparative Example 4, although the flatness was good, pleats were generated at the stage of prebaking. As described above, all of the characteristics can be satisfied only when a certain amount is used as an essential component of the epoxy compound having a site for bonding a decane. [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.

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Claims (20)

A thermosetting composition comprising a polyester phthalic acid, an epoxy compound having a siloxane coupling site, an epoxy compound having no siloxane coupling site, and an epoxy curing agent. It is characterized in that the polyester proline is obtained by reacting a tetracarboxylic dianhydride, a diamine, and a polyvalent hydroxy compound as essential raw material components, and by using X-mol of the tetracarboxylic acid A polyester phthalic acid obtained by reacting the dianhydride, the diamine of Y mole, and the polyvalent hydroxy compound of Z mole by a ratio of the following formula (1) and formula (2), 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); the epoxy compound having a siloxane coupling site and the epoxy having no siloxane coupling site with respect to 100 parts by weight of the polyester phthalic acid The total of the compounds is from 20 parts by weight to 400 parts by weight; based on 100 parts by weight of the total of the epoxy compound, Oxygen 0 parts hardener by weight to 60 parts by weight; and the total amount of the epoxy compound having a siloxane silicon bonded portion epoxy compound ratio of 0.5 wt% to 70 wt%, R ¹ is a tetracarboxylic dianhydride residue, R ² is a diamine residue, and R ³ is a residue of a polyvalent hydroxy compound. The thermosetting composition according to claim 1, wherein the raw material component of the polyester proline further comprises a monohydric alcohol. The thermosetting composition according to claim 2, wherein the monohydric alcohol is selected from the group consisting of isopropanol, allyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, propylene glycol monoethyl ether, and 3-ethyl. More than one of the group 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 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, One or more of 4-butane tetracarboxylic dianhydride and ethylene glycol bis(hydrogen trimellitate). 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 of phenoxy)phenyl]indoles. 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. And one or more 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 epoxy compound having a siloxane coupling site is selected from the group consisting of a compound represented by the following formula (5) and a formula ( 6) at least one of the group of compounds represented, R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydroxyl group, an organic group having 1 to 26 carbon atoms, or an organic group having an epoxy group, and R ^{7 is} independently hydrogen and an organic group having 1 to 26 carbon atoms. Or an organic group having an epoxy group, at least one of R ⁴ , R ⁵ , R ⁶ and R ⁷ is an organic group having an epoxy group, m is an integer of 2 or more, and R ⁴ or R ⁵ may also bond with R ⁴ or R ⁵ on different Si bonds to form a oxoxane ring, and R ⁶ and R ⁷ may also bond to form a oxane ring; R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently hydrogen or an organic group having 1 to 26 carbon atoms, and R ¹² and R ¹³ are each independently hydrogen, an organic group having 1 to 26 carbon atoms or having an epoxy group. The organic group, at least one of R ¹² and R ¹³ is an organic group having an epoxy group, n is an integer of 1 or more, and R ⁸ or R ⁹ may be bonded to R ⁸ , R ⁹ bonded to different Si, R ¹⁰ or R ^{11 is} bonded to form a oxoxane ring, and R ¹⁰ or R ¹¹ may be bonded to R ⁸ , R ⁹ , R ¹⁰ or R ¹¹ bonded to different Si to form ruthenium. Oxygen ring. The thermosetting composition according to claim 1 or 2, wherein the epoxy compound having a siloxane coupling site is selected from the group consisting of 1,3-bis[2-(3, 4-epoxycyclohexyl)ethyl]tetramethyldioxane, 1,3-bis(3-glycidoxypropyl)tetramethyldioxane, 3-glycidoxypropyl a copolymer obtained by reacting trimethoxydecane as a raw material component, and reacting by using 3-glycidoxypropyltrimethoxydecane, phenyltrimethoxydecane, and trimethylmethoxydecane as raw materials And at least one of the group consisting of the obtained copolymers. 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 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride or 1,2,3 a 4-butane tetracarboxylic dianhydride; the diamine is 3,3'-diaminodiphenyl hydrazine; the polyvalent hydroxy compound is 1,4-butanediol; and the oxirane bond The epoxy compound at the junction is a copolymer having a weight average molecular weight of 1,000 to 200,000 obtained by reacting 3-glycidoxypropyltrimethoxydecane as a raw material component; the non-doped alkane bond The epoxy compound at the site is 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-1,1-bis[4-([2,3-epoxypropane) Oxy]phenyl)ethyl]phenyl]propane; the epoxy hardener is trimellitic anhydride or 2-undecylimidazole; and further contains methyl 3-methoxypropionate or propylene glycol monomethyl ether The acid ester acts as a solvent. A cured film obtained by the thermosetting 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 liquid crystal display element using the color filter described in 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 liquid crystal 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 liquid crystal 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 device using the cured film described in claim 13 as a transparent insulating film formed on a transparent electrode. A light-emitting diode illuminant using the cured film described in claim 13 as a protective film.