TW201107406A - Polyester composition for forming thermoset film - Google Patents

Abstract

Provided is a polyester composite for forming thermoset films, said composite having, after forming a thermoset film, high resistance to solvents and heat, good liquid crystal orientation, high transparency, and high planarizability. Said composite can also, when forming a thermoset film, be dissolved in glycol solvents and lactate ester solvents that can be applied to production lines for planarized color filter films. The composite contains: a component (A) which is a polyester obtained by reacting a tetracarboxylic dianhydride with a diol compound; a component (B) which is an epoxy compound having at least two epoxy groups; and a component (C) which is an amino-group-containing carboxylic compound obtained by reacting a diamine compound, a dicarboxylic anhydride, and a tetracarboxylic dianhydride.

Description

[Technical Field] The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained from the composition. More specifically, the present invention relates to a polyester composition for forming a thermosetting film having high transparency and flatness, and having liquid crystal alignment ability, high solvent resistance and heat resistance, and a cured film thereof, and Use this hardened film. The polyester composition for forming a thermosetting film is particularly suitable for a color filter coating agent having a liquid crystal alignment function in a liquid crystal display. [Prior Art] Generally, an optical device such as a liquid crystal display element, an organic EL (electroluminescent) element, or a solid-state imaging element is provided with a protective film in order to prevent the surface of the element from being exposed to a solvent or heat during the manufacturing step. This protective film not only needs to have high adhesion to the substrate to be protected, but also has high solvent resistance, and also requires properties such as transparency and heat resistance. When the protective film is used as a protective film for a color filter for a color liquid crystal display device or a solid-state imaging device, it is generally required to have a flattening effect of a color filter or a black matrix resin of the underlying substrate, that is, as a planarization. Membrane properties. In particular, when manufacturing a color liquid crystal display element of the STN type or the TFT type, it is necessary to make the bonding precision between the color filter substrate and the counter substrate very tight, and it is indispensable to make the cell gap between the substrates uniform. Further, in order to maintain the transmittance of light transmitted through the color filter, the planarizing film of the protective film must have high transparency. In addition, in recent years, due to the introduction of phase difference [ -5- 201107406 materials in the liquid crystal display to achieve low cost and light weight, such phase difference materials are generally coated with liquid crystal monomers, and after alignment, A material that hardens light. In order to align the phase difference material, it is necessary to have an alignment material after the underlayer film is rubbed. Therefore, a liquid crystal alignment layer film is formed on the coating layer of the color filter, and a phase difference material is formed (see Fig. 2(a)). When a film having a coating layer of the liquid crystal alignment layer and the color filter (see Fig. 2(b)) can be formed, such a material is strongly expected from the viewpoints of cost reduction and a large number of processes. Generally, the coating layer of the color filter is made of an acrylic resin having high transparency. As the acrylic resin, a glycol solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate or an ester solvent such as ethyl lactate or butyl lactate can be widely used from the viewpoint of safety and handling properties. This acrylic resin is thermally or photohardened to impart heat resistance or solvent resistance (Patent Documents 1, 2). However, the conventional thermosetting or photocurable acrylic resin exhibits moderate transparency or flatness, but even if the flat film is rubbed, it does not exhibit sufficient alignment. Further, as the liquid crystal alignment layer, a material composed of a solvent-soluble polyimine or poly-proline is generally used. These materials have been reported to have sufficient solvent resistance by rubbing imitation at the time of post-baking, and have been reported by rubbing treatment (Patent Document 3). However, when viewed as a planarizing film of a color filter, there are problems such as flatness and transparency being greatly lowered. Further, polyimine or polylysine is soluble in a solvent such as N-methyl-2-pyrrolidone or butyrolactone, but has low solubility in a glycol solvent or an ester solvent, and is difficult to apply to production. A production line for planarizing films. 201107406 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and a problem to be solved is to provide a solvent-resistant film which exhibits high solvent resistance and liquid crystal. Ordination, heat resistance, high transparency, and high flatness, and a glycolic solvent or a lactic acid ester solvent which can be used in the production line of a flattening film which can be dissolved in a color filter when the cured film is formed. material. [Means for Solving the Problems] The inventors of the present invention have found the present invention in order to solve the above problems. In other words, the first aspect relates to a polyester composition for forming a thermosetting film, which comprises (A) component, (B) component, and (C) component, and (A) component: tetracarboxylic dianhydride and diol Polyester (B) obtained by reacting a compound: an epoxy compound having two or more epoxy groups, and (C) a component: an amine group obtained by reacting a diamine compound, a dicarboxylic anhydride, and a tetracarboxylic dianhydride Carboxylic acid compound. The second aspect is the polyester composition for forming a thermosetting film according to the second aspect, wherein the component (A) is a polyester containing a structural unit represented by the following formula (1).

L SJ -7- 201107406 【化1】 {HOOC, /COOH \ . -Π*"〇-Β+ (" ° ° / (wherein, A is a tetravalent organic group having four linkages bonded to an alicyclic group or an aliphatic group, and B is represented by an alicyclic group. The present invention relates to a polyester composition for forming a thermosetting film according to the first or second aspect, wherein the component (A) is as follows a polyester obtained by reacting a tetracarboxylic dianhydride represented by the formula (i) with a diol compound represented by the formula (Π) [Chemical 2]

(In the formula, 'A is a tetravalent organic group having four bonding bonds bonded to an alicyclic group or an aliphatic group, and B is a combination of two bonding bonds on an alicyclic group or an aliphatic group. The valence organic group) is a polyester composition for forming a thermosetting film according to the second or third aspect, wherein in the above formula (1), the system A represents a formula (A-1) to (A) -8) a group of at least one selected from the group, and b is a group selected from at least one of the groups represented by the following formulas (B-1) to (B-5). 201107406 [A3] (A-1) [A-2 cf3 (A.3) (A-4) X xn: (A-5) (A-6) (A-7) (A-8) 4: λ B_1 (B-2) (B-3) B-4: (B-5) The fifth aspect is a polyester composition for forming a thermosetting film according to any one of the first to fourth aspects, wherein The weight average molecular weight of the polyester of the component A) is from 1,000 to 30,000 in terms of polystyrene. The sixth aspect is the polyester composition for forming a thermosetting film according to any one of the first to fifth aspects, wherein the component (C) is 1 mol with respect to the tetracarboxylic dianhydride, and the diamine compound 2 is a molar The amine-containing carboxylic acid compound obtained by the 2 molar reaction of the dicarboxylic anhydride. The polyester composition for forming a thermosetting film according to any one of the first to fifth aspects, wherein the component (C) is a compound represented by the following formulas (iii), (iv) and (v) The obtained amino group-containing carboxylic acid compound-9- 201107406 [Chemical 5]

H2n-p-νη2 ο (Ni) (In the above formulas (iii) and (iv), the Ρ and Q systems each independently represent a divalent organic group, and in the formula (v), the Z system represents a tetravalent organic group). The eighth aspect is a polyester composition for forming a thermosetting film according to any one of the first to seventh aspects, wherein the component (B) is contained in an amount of from 3 to 50 parts by mass based on 1 part by mass of the component (A). 5 to 80 parts by mass of the component (c). The ninth aspect is the polyester composition for forming a thermosetting film according to any one of the first to eighth aspects, which further comprises a bismaleimide compound as the component (D). The first aspect is the polyester composition for forming a thermosetting film according to the ninth aspect, wherein the component (D) is contained in an amount of from 5 to 50 parts by mass based on 100 parts by mass of the component (A). The eleventh aspect relates to a cured film obtained by using the polyester composition for forming a thermosetting film according to any one of the first to tenth aspects. The present invention relates to a liquid crystal alignment layer which is obtained by using the polyester composition for forming a thermosetting film according to any one of the first to the first aspects of the invention. [Effect of the invention] The polyester for forming a thermosetting film of the present invention The material can be formed into a material for forming a liquid crystal alignment film or a planarizing film, in addition to a cured film having high crystallinity, high transparency, high solvent resistance, and high heat resistance, and having liquid crystal alignment energy. In particular, the "liquid crystal alignment layer" having the characteristics of both the liquid crystal alignment film and the color filter layer which are formed independently in the past can be formed at one time, and the manufacturing process can be simplified and the number of processes can be reduced. . Further, since the polyester composition for forming a thermosetting film of the present invention is soluble in a glycol solvent and a lactic acid ester solvent, it can be suitably used in a production line for a planarizing film mainly using such a solvent. [Embodiment of the Invention] As described above, the acrylic resin and the polyimide film of the conventionally proposed cured film cannot sufficiently satisfy the flatness, transparency, alignment, and the like required for the liquid crystal alignment film or the planarizing film. All performance. In addition, it has been proposed to use polyester as an alignment material for a liquid crystal display element (see Japanese Patent Laid-Open No. Hei 5-158055, JP-A-2002-22903-9), but none of them have thermosetting properties. The film has poor solvent resistance. The present invention is characterized in that the use of a thermosetting polyester is attempted to improve the above-described performance. In other words, the present invention relates to a polyester containing (A) component, an epoxy compound having two or more epoxy groups of (B) component, A polyester composition for forming a thermosetting film of an amino group-containing carboxylic acid compound of the component (C). Further, 'the present invention is a thermosetting hardened -11 - 201107406 film forming polyester which may contain a bismaleimide compound as the component (D) in addition to the component (A), the component (B) and the component (C). Things. Hereinafter, the details of each component will be described. [Component (A)] The polyester of the component (A) is preferably a polyester containing a structural unit represented by the following formula (1), more preferably a polyester composed of a structural unit represented by the formula (1). . [6] / HOOC, /COOH \ 十-OBJ- (1) \ ° ° In the above formula, A represents a tetravalent organic group having four bonding bonds bonded to an alicyclic group or an aliphatic group. B is a divalent organic group having two bonding bonds bonded to an alicyclic group or an aliphatic group. The above A is preferably a group represented by the following formula (ιΑ1), formula (1A2) or formula (1A3). (1) A1 represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, and more preferably Preferably, it is a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms, wherein any hydrogen atom contained in the A1 group may be independently substituted with an aliphatic group, or two of them may be bonded to each other to form a hydrogen atom. 4~6 member ring. Here, the aliphatic group of the substituent is preferably a carbon number of aliphatic-12-201107406. A fatty group 9 is more preferably an aliphatic group having 1 to 3 carbon atoms. When a ring is formed, a condensed polycyclic hydrocarbon group in which one or all of the bridged cyclic hydrocarbon groups such as a norbornene group or an adamantyl group are hydrogenated. In the above formula, R1 represents a single bond, a condensed group, an ether group, and a commercially available a saturated hydrocarbon group having 1 to 8 atomic number or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted by a fluorine atom, preferably a single bond, a carbonyl group, an ether group, a sulfonyl alcohol group, and a saturated carbon number of 1 to 5. A hydrocarbon group or a saturated hydrocarbon group having 1 to 5 carbon atoms which is substituted by a fluorine atom. R2 represents a saturated hydrocarbon group having 1 to 8 carbon atoms. Preferably, it is a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 3 carbon atoms, and a tetravalent organic group in the formula (1). A preferred specific example of A is represented by the following formula (A-1: ) - formula (A-8). Among the groups represented by the following formula (Α-1). ~ formula (A-8), A is preferably It is a group selected from the formula (Α·1 ) or (A -2 ).

XX (A*1 ) (A-2) (A-3) (A-4)

(A-7) (A-8) (A-5) (A-6) In the above formula (1), B represents a divalent organic compound having two linked bonds bonded to an alicyclic group or an aliphatic group. The group is preferably a group represented by the following formula (1B1) or formula (1B2). 201107406 - r4-b1{r3-b1)^r5 - R6-B2-R7- (1B1) (1B2) wherein B1 represents a cyclic saturated hydrocarbon group, preferably represents a carbon number of 4~ The cyclic saturated hydrocarbon group of 8 is more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the B1 group may be independently substituted with an aliphatic group. The aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are combined to form a ring, for example, it is a norbornene group or A crosslinked cyclic hydrocarbon group such as an adamantyl group, or a partially or wholly hydrogenated condensed polycyclic hydrocarbon group, wherein B2 represents a phenylene group, and R3 represents a single bond 'carbonyl group, an ether group, a sulfonyl group, a carbon atom. The saturated hydrocarbon group of 1 to 8 or the saturated hydrocarbon group having a carbon number substituted by a fluorine atom is preferably a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a fluorine atom. a saturated hydrocarbon group having a carbon number of 5, and r4 and R5 each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms. And an alkyl group having 1 to 3 carbon atoms. r6 and R7 each independently represent an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms. Further k represents 〇 or ^. A preferred specific example of B of the divalent organic group in the formula (1) is represented by the following formula (B-1) to formula (B-5). The following formula (B-1) to formula (B-5) are given. In the group shown by -14- 201107406, B is preferably a group selected from the group consisting of the formula (Β-1) to (B-4).

(B-1) (B-2) (B-3) (B-4) (B-5) The polyester of the component (A) is preferably a formula (in the structural unit shown by Π, A is preferably It has at least one structure selected from the group consisting of the groups represented by the formula (1A1) to the formula (1A3), but may have a structure other than the group represented by the formula (1A1) to the formula (1A3). In the structure in which the polyester is formed, the structure is not particularly limited, but is preferably a structure selected from at least one of the groups represented by the following formulas (1A4) to (1A5). (1A4) (1A5) In the above formula, R8, R9 and R1() each independently represent a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a carbon atom substituted by a fluorine atom. The number of saturated hydrocarbon groups preferably represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom. Preferably, it represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom, and R9 preferably represents an ether group or a carbon atom. Number of 1 to 5 saturated hydrocarbons Or a saturated hydrocarbon group having 1 to 5 carbon atoms which is substituted by a fluorine atom, and R1Q is preferably a saturated hydrocarbon group having a carbon number of 1 to 5, which is a carbonyl group, an ether group or a sulfonyl group, and a carbon atom substituted by a fluorine atom. A saturated hydrocarbon group having an atomic number of 1 to 5. Further, h represents 0 or 1. Preferred examples of the above formula (1A4) to formula (1A5) are represented by the following formula (al) to formula (a7).

XX (»1) (a2) (a3) (a4) (a6) (aS) (a7) In the polyester of the component (A) used in the present invention, in the structural unit represented by the above formula (1) And A is preferably a weight average molecular weight of a polyester containing at least 60 mol% or more of a structural unit selected from the group consisting of the groups represented by the formula (1A1) to the formula (1A3) (A). It is preferably 1 000 to 3 0000, more preferably ι, 5 〇〇 1 〇, 〇〇〇. When the weight average molecular weight of the polyester of the component (A) is less than the above range, the alignment property and the solvent resistance tend to be lowered, and if it exceeds the above range, the planarization property may be lowered. <Production Method of Component (A)> In the present invention, the polyester of the component (A) can be obtained, for example, by polymerizing a tetracarboxylic dianhydride and a monool compound. More preferably, a tetracarboxylic dianhydride (hereinafter referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol compound containing a diol compound represented by the following formula (11) (hereinafter also referred to as a diol component) is obtained by a reaction. -16- 201107406 【化1 3】

In the above formula, 'A and B are the same as defined in the above formula (1), and the preferred form is the same as the above. In the present invention, the tetracarboxylic dianhydride represented by the formula (i) and the diol compound represented by the formula (ii) may be used alone or in combination of two or more. The polyester of the above (A) component is not limited to the tetracarboxylic dianhydride represented by the above formula (i) as an acid component, and may be used in addition to the tetracarboxylic dianhydride (hereinafter also referred to as other acid II). anhydride). In this case, the other acid dianhydride is not particularly limited as long as it does not affect the effects of the present invention. The tetracarboxylic dianhydride represented by the following formula (i2) is preferred. 【化1 4】 Ο 〇

UX °OwO° {i2) τ τ ο ο Here, the W of the above formula (i2) is selected from the group represented by the formula (1A4) and the formula (1A5) defined in the above formula (1). As for one configuration, R8, R9, R1G, h are also as defined above. Further, preferred specific examples of the formula (1A4) and the formula (i A5) are as shown in the above formula (al) - formula (a7). In the present invention, the tetracarboxylic dianhydride represented by the formula (i) preferably contains at least 60 mol% or more of the acid component. -17- 201107406 In the polyester of the above component (A), the total ratio of the tetracarboxylic dianhydride (the total amount of the acid components) to the total amount of the diol compound (the total amount of the diol compound) is (The total number of moles of the diol compound) / (the total number of moles of the tetracarboxylic dianhydride compound) is preferably from 0.5 to 1.5. As with the general polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the resulting polyester, and the higher the molecular weight. The polyester of the component (A) is designed to avoid a decrease in the stability of storage. The anhydride end is preferred. The end of the polyester varies depending on the blending ratio of the acid component to the diol component. For example, when the acid component is excessively reacted, the terminal tends to be an acid anhydride. When the diol component is excessively polymerized, the terminal tends to be a hydroxyl group. At this time, the terminal hydroxyl group is reacted with a carboxylic acid anhydride, and the terminal hydroxyl group can be blocked with an acid anhydride. Such carboxylic anhydrides are, for example, phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methyl- 1,2-cyclohexanedicarboxylic anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, A Tetrahydrophthalic anhydride, bicyclo[2.2.2]octene-2,3-dicarboxylic anhydride, and the like. In the production of the polyester of the component (A), the reaction temperature of the acid component and the diol component may be any temperature of 50 to 200 ° C, preferably 80 to 170 ° C. For example, a polyester can be obtained at a reaction temperature of 100 to 140 ° C and a reaction time of 2 to 48 hours. Further, the reaction temperature at which the terminal hydroxyl group is protected by an acid anhydride may be selected from the range of -18 to 201107406 50 to 200 ° C, preferably 80 to 17 ° C. The reaction of the above acid component with the diol component is generally carried out in a solvent. In this case, the solvent which can be used is not particularly limited as long as it does not contain a functional group which reacts with an acid anhydride such as a hydroxyl group or an amine group. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone 'N-vinylpyrrolidinium, N-methylcaprolactam, Dimethyl sulfonium 'tetramethyl urea, dimethyl hydrazine, hexamethyl hydrazine, m-cresol, r-butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone ' 2 -heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate 'methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate' Ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, and the like. These solvents may be used singly or in combination, but are more preferably propylene glycol monomethyl ether acetate from the viewpoint of safety and suitability of a coating line of a color filter. Further, even if the solvent of the polyester is not dissolved, it may be used in combination with the above solvent within a range in which the polyester formed by the polymerization reaction does not precipitate. Further, a catalyst may be used in the reaction of the above acid component (formula (i) and formula (i2)) with a diol component (formula).

Specific examples of the catalyst used in the polymerization of the polyester include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, and benzyltrimethyl bromide. Ammonium, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide Quaternary ammonium salt, tetraphenyl chlorinated chloride, tetraphenyl bromide, benzyltriphenyl chlorinated chloride, benzyltriphenylphosphonium bromide, ethyl chloride [SI -19- 201107406 Grade 4 scale salts such as triphenyl scale and ethyl bromide bromine. The solution containing the polyester of the component (A) obtained above can directly prepare a polyester composition for forming a thermosetting film. Further, it can be used after it has been recovered by sinking a weak solvent such as methanol, ethanol, diethyl ether or hexane. <Component (B)> The component (B) of the present invention has two or more epoxy compounds, for example, tris(2,3-epoxypropyl)trimeric isocyanide 1,4-butanediol Diglycidyl ether, 1,2-epoxy-4-(epoxycyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-oxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid, di-, 4,4'-methylenebis(Ν,Ν-二Glycidyl aniline, 3,4 cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, trimethylol glycol glyceryl ether and bisphenol-indole-diglycidyl ether and pentaerythritol condensation Ether, etc. In addition, from the viewpoint of the availability of the commercially available product, the specific example (product name) may be used, but it is not limited thereto: YH4 3 4L (manufactured by Tohto Kasei Co., Ltd.) has an amine group. Equivalent epoxy resin; Epolead GT-401, Epolead GT-403, Epolead, Epolead GT-302, Celoxide 2 0 2 1 , Celoxide Daicel Chemical Industry Co., Ltd., etc.; epoxy resin with cyclohexene oxide; Epikote 1001 ' Epikote 1002, Epikote for esters in water, epoxidized esters; ethyl ether ethers, (2,3-ring: glyceride-epoxy, alkane triglycidyl, YH -434 Epoxy Tree GT-301 3000 (丨1, 003, -20- 201107406

Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, oiled Shell Epoxy (now Japan Epoxy Re sin)), etc. Epikote 807 (oil) Shell Epoxy (now Japan Epoxy Resin Co., Ltd.) and other bisphenol F-type epoxy resin; Epikote 152' Epikote 154 (above, oiled Shell Epoxy (shares) (now Japan Epoxy Resin (shares) No.), EPPN 201, EPPN 202 (above, manufactured by Nippon Chemical Co., Ltd.), etc.; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1 020, EOCN-1 025 , EOCN- 1 027 (above, 曰本化药(股))'Epikote 180S75 (oiled Shell Epoxy (now Japan Epoxy Resin)), etc. Deancol EX-252 (made by Nagase Chemtex), CY175, CY177, CY179, Araldite CY-182 'Araldite CY-192, Araldite CY-184 (above, CIBA-GEIGY AG), Epiclon 200, Epiclon 400 (above, Dainippon Ink Chemical Industry (shares) (now DIC (shares) ) Ltd.) 'Epikote 871' Epikote 872 (above, Yuka Shell Epoxy (shares) (now Japan Epoxy Resin (shares), Ltd.)), ED - 5 66 1, ED - 5 66 2 (or more,

Epoxy epoxy resin such as Cel an es Coating; Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX -522, an aliphatic polyglycidyl ether such as Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321 (manufactured by Nagase Chemtex (stock: -21-07406)). Further, a compound having at least two epoxy groups may use a polymer having an epoxy group. Such a polymer can be used as long as it has an epoxy group, and is not particularly limited. The above epoxy group-containing polymer can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl acrylate, copolymer of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and copolymer of styrene and 2-hydroxyethyl methacrylate, etc. A polycondensation polymer such as an addition polymerization polymer or an epoxy novolac. Or the above epoxy group-containing polymer can be produced by a reaction of a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate. The weight average molecular weight of such a polymer is, for example, 300 to 200,000. The epoxy compound having two or more of these epoxy groups may be used singly or in combination of two or more. The content of the epoxy compound having two or more epoxy groups in the component (B) in the polyester composition for forming a thermosetting film of the present invention is preferably 1 part by mass based on the polyester of the component (A). It is 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass. When the ratio is too small, the solvent resistance or heat resistance of the cured film obtained from the polyester composition for forming a thermosetting film is lowered, and when it is too large, the solvent resistance may be lowered or the storage stability may be lowered. -22-201107406 <(c) component> The component (C) is an amino group-containing carboxylic acid compound obtained by reacting a diamine compound, a dicarboxylic acid anhydride, or a tetracarboxylic dianhydride. The details are the amino group-containing carboxylic acid compound obtained by reacting the diamine compound 2 mole with the dicarboxylic anhydride 2 mol with respect to the tetracarboxylic dianhydride 1 mol. The diamine compound, the dicarboxylic anhydride, and the tetracarboxylic dianhydride are, for example, compounds represented by the following formulas (iii) to (v). [化1 5]

H2n-p-nh2 0 (iii) In the above formulas (iii) and (iv), the P and Q systems each independently represent a divalent organic group, and in the formula (v), the Z system represents a tetravalent organic group. Therefore, the diamine compound represented by the above formula (iii), the dicarboxylic anhydride represented by the formula (iv) and the tetracarboxylic dianhydride represented by the formula (v) can be reacted to obtain a compound represented by the following formula (2). 【化1 6】 Ο HOOC, person

N _ Η Η / \ Η HOOC COOH Ο (2)

P, human 〆COOH N H In the formula (2), the P, Q, and Z systems are the same as defined in the above formula (iii), formula (iv), and formula (v). In the present invention, the diamine compound, the dicarboxylic anhydride, and the tetracarboxylic dianhydride may be used singly or in combination of plural kinds. Therefore, the amino group-containing carboxylic acid compound of the component (C[S] -23- 201107406) of the present invention may be used alone or in combination of a plurality of compounds represented by the formula (2). Among the above P and Q, preferred are divalent organic groups each having a ring structure. Here, the ring structure is, for example, a benzene ring, an alicyclic ring or a condensed polycyclic hydrocarbon. In the formula (iii), the ring structure of 'P is preferably a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, and a carbon number. Condensed polycyclic hydrocarbons of 7 to 16. Therefore, specific examples of the diamine compound having such a ring structure include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-di Aminotoluene, 2,4-dimethyl-1,3-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl- 1,4 -diaminobenzene, 2.4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoxyxylenol, 2,5-diaminobenzoic acid, 3,5 -diamine benzoic acid, N,N-diallyl-2.4-diaminoaniline, N,N-diallyl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 2-(3-aminophenyl)ethylamine, 1,5-naphthalenediamine, 2,7-naphthalene Diamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy, 4,4'-diaminobiphenyl, 3,3 '-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3,-difluoro-4,4'-diamine Biphenyl, 2,2'-trifluoromethyl-4,4 '-Diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diamino Diphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-di Amine-24- 201107406 bisdiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenylamine, 3,3'-Diaminodiphenylamine, 3,4'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl ( 3,3'-Diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, 4,4'-diaminobenzophenone, 3,3' -diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzamide, 1,2-bis(4-aminophenyl)ethane 1,2-bis(3-aminophenyl)ethane, 4,4'-diaminotolane (diaminotolane), 1,3-bis(4-aminophenyl)propane, 1,3 - bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3- Amine -4 -methylphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-dual ( 3-amino-4-methylphenyl)hexafluoropropane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1 , 5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)decane, 1,10-bis(4-aminophenoxy)decane 1,11-bis(4-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, bis(4-aminophenyl)propane II Acid ester, bis(4-aminophenyl)butane dicarboxylate, bis(4-aminophenyl)pentane dicarboxylate, bis(4-aminophenyl)hexanedicarboxylate, bis( 4-aminophenyl)heptane diester, bis(4-aminophenyl)octane dicarboxylate, bis(4-aminophenyl)decanedioate, bis(4-aminobenzene) Base decane diester, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-amine Phenyloxy)[s] -25- 201107406 Benzene '1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminobenzyl)benzene, 1,3- Bis(4-aminobenzyl)benzene, bis(4-aminophenyl)p-phthalate, bis(3-aminophenyl)p-phthalate, bis(4-aminophenyl) Phthalate, bis(3-aminophenyl) metacaprate, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3) -aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methyl Ketone], 1,4-phenylene bis(4-aminobenzoate), 1,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylene bis ( 4-amino benzoate), 1,3-phenylene bis(3-aminobenzoate), N,N'-(1,4-phenylene) bis(4-aminobenzene) And decylamine, N,N'-(1,3-phenylene)bis(4-aminobenzophthalamide), N,N'-(1,4-phenylene)bis(3-amine Benzobenzamine), N,N'-(1,3-phenylene)bis(3-aminobenzoguanamine), bis(4-aminophenyl)-p-amine, double (3 -aminophenyl) pair Indoleamine, bis(4-aminophenyl)m-decylamine, bis(3-aminophenyl)m-decylamine, 2,2-bis[4-(4-aminophenoxy)· Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2 ,6.diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7- Diaminodibenzofuran, 3,6-diaminodibenzofuran, 2,6-diaminocarbazole, 2,7-diaminocarbazol, 3,6-diaminocarbazole, 2,4-Diamino-6-isopropyl-1,3,5-triazine, 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole, 1,4 -diaminocyclohexane, 1,3-diaminocyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, and the like. Further, in the above formula (iv), the ring structure of Q is preferably a benzene ring -26-201107406, an alicyclic ring having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms. More preferably an alicyclic ring. Specific examples of the dicarboxylic acid anhydride having such a ring structure include, for example, phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornate _2,3-dipic acid In the above formula (ν), ruthenium, itaconic anhydride, tetrahydrofurfuric anhydride, etc., Ζ is preferably a tetravalent organic group having a ring structure. Here, the ring structure is, for example, a benzene ring, an alicyclic ring or a condensed polycyclic hydrocarbon. More preferably, the tetravalent organic group having four bonding bonds bonded to the alicyclic group or the aliphatic group is more preferably a formula (Ζ-1), a formula (Ζ-2) or a formula (Ζ-3) The base of expression. [化1 7]

(Ζ-1) (Ζ-2) (Ζ-3) wherein Ζ1 represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably 4 to 4 carbon atoms. a cyclic saturated hydrocarbon group of 6. Any of the hydrogen atom groups contained in the 'Ζ1 group may be independently substituted with an aliphatic group, or two of them may be bonded to each other to form a 4 to 6 member ring. Here, the aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are combined to form a ring, for example, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantyl group is a hydrogenated condensed polycyclic hydrocarbon group. In the above formula, Υ1 represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms of carbon-27-201107406 or a saturated hydrocarbon group having 1 carbon atom substituted by a fluorine atom. Preferred are a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group of carbon H 1 to 5 or a group having 1 to 5 carbon atoms which are substituted by a fluorine atom. Y2 is a saturated hydrocarbon group having 1 to 8 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. ) ~ formula (A-8). Particularly preferred is a group selected from the group consisting of formula (A-1) or (A-2). The tetracarboxylic dianhydride represented by the formula (v) is, for example, pyromellitic acid '2,3,6,7-naphthalene tetraresidic acid dianhydride, 1,2,5,6-naphthalene tetraphthalic acid dianhydride, ι , 4 naphthalene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, thiotetrahydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2 ,,3,3,_Biphenyltetracarboxylic anhydride ' 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3,4,4,_dibenzoic acid dianhydride, 2 , 3,3',4'-benzophenone tetracarboxylic dianhydride, bis(3,4-phenylene)methane dianhydride, bis(3,4-dicarboxyphenyl) acid dianhydride, 3,4 -Dicarboxyphenyl) Maple dianhydride, 2,2-bis(3,4-di-resin phenyl phthalic anhydride' 2,2-bis(3,4-dimercaptophenyl) hexafluoropropyl Anhydride, dicarboxymethyl-p-phthalic acid dianhydride, 4,6-dicarboxymethylisophthalic acid di 4-(2,5-dioxotetrahydro-3-indolyl) phthalic anhydride, 1,4_ Bis(2,5-tetrahydro-3-furanyl)benzene, 1,4-bis(2,6-dioxotetrahydro-4-pyranyl' 1,4-bis(2,5-dioxotetrahydro) -3-methyl-3-furanyl)benzene, 14_ 2,6--oxytetramine-4-methyl-4-pyrenepyranyl)benzene, i,2,3,4-dinary four liver 1,2,3,4 - Circulating Hospital, tetracarboxylic acid, liver, 1, 2 _ dimethyl hydrazine, 2,3 butane tetracarboxylic dianhydride, 1,3-dimethyl-l, 2,3,4-cyclobutane tetracarboxylic acid ~ 8 子 number and hydrocarbon Atomic hydrazine, dianhydride, 5,8-carboxylic acid ketone ketone tetracarboxylic bis( )propane 2,5-anhydride, dioxy)benzene bis (carboxylic acid, 4-cyclo dianhydride-28- 201107406, 1,2 , 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5 - tetrahydrofuran tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 4-(2.5-dioxotetrahydro- 3·furanyl)-cyclohexane-1,2-dicarboxylic anhydride, 5-(2.5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-indole, 2-di Carboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3,4-dicarboxy· 1,2,3,4-tetrahydro-1-naphthalene Succinic dianhydride, 3,4-dicarboxy-12,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, bicyclo[3.3.0]octane-2,4,6,8 -tetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride '2,3,5,6-norbornanetetracarboxylic dianhydride, 3,5,6-tricarboxyl Norbornane-2-furic acid dianhydride, tricyclo[4.2.1.02,5]decane-3,4,7,8-four Acid dianhydride, tetracyclo[4.4.1.02,5.07,1()]undecane-3,4,8,9-tetracarboxylic dianhydride, hexacyclo[6.6.0.12'7.03, 6.19'丨4.〇 1(), 13] hexadecane-4,5,11,12-tetracarboxylic dianhydride, 1,4-bis(2,5-dioxotetrahydro-3-furanyl)hexane, 4-double (2,6-Dioxytetrahydro-4-pyranyl)hexane or the like. In the production of the compound of the above component (C), the reaction temperature of the tetracarboxylic dianhydride and the diamine compound and the dicarboxylic anhydride may be any temperature of 5 to 50 ° C, preferably 10 to 35 ° C. In the reaction, in order to avoid polymerization, first, after dissolving the diamine compound in any solvent, in order to avoid polymerization due to heat generation during the reaction, it is more preferable to add tetracarboxylic dianhydride and water to a temperature of 23 ° C. Dicarboxylic anhydride The above reaction is generally carried out in a solvent. The solvent which can be used at this time is not particularly limited as long as it does not contain a functional group which reacts with an acid anhydride such as a hydroxyl group or an amine group. For example, there are N,N-dimethylformamide, N,N-dimethylethyl [s ] -29- 201107406 decylamine, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methyl Caprolactam, dimethylimidazole 'dimethylimine mill, tetramethyl urea, dimethyl mill, hexamethyl sulfoxide, m-cresol, butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, Methyl isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3-methyl Ethyl oxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, methyl cellosolve acetate, ethyl solubilized fiber Acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, cyclohexanol, ethyl acetate, butyl acetate, Ethyl lactate, butyl lactate, and the like. These solvents may be used singly or in combination, but from the viewpoint of solubility, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, hydrazine, hydrazine dimethyl acetamide, hydrazine-methyl group are preferred. 2-pyrrolidone, dimethylimidazole. Further, even a solvent which does not dissolve the amino group-containing carboxylic acid compound may be used in combination with the above solvent within a range in which the amino group-containing carboxylic acid compound formed by the polymerization reaction does not precipitate. The content of the component (C) in the polyester composition for forming a thermosetting film of the present invention is preferably from 5 to 80 parts by mass, more preferably from 5 to 60 parts by mass based on 100 parts by mass of the polyester polymer of the (Α) component. Parts by mass. When the ratio is too small, the alignment property of the cured film obtained from the polyester composition for forming a thermosetting film is lowered, and when it is too large, the transmittance may be lowered or the flatness may be lowered. <Component (D)> In the present invention, a compound of the double-Malaysia -30-201107406 amine represented by the following formula (3) may be contained as the component (D). The bismaleimide compound of the component (D) can further improve the planarization property. [化1 8]

In the formula, X is an organic group selected from the group consisting of an aliphatic group, an organic group having a cyclic structure and an aromatic group, or a combination of a plurality of organic groups selected from the group. Further, X may also contain a bond such as an ester bond, an ether bond, a guanamine bond or a urethane. Such a bismaleimide compound is, for example, 1^,&gt;1'-3,3-diphenylmethane bismaleimide, &gt;1,:^'-(3,3-diethyl -5,5-dimethyl)-4,4-diphenyl-methane bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, 3,3- Diphenyl maple bismaleimide, 4,4-diphenylfluorene bismaleimide, anthracene, Ν'-p-benzophenone bismaleimide, N, N, - II Ethyl benzene bismaleimide, N,N,-diphenyl ether bismaleimide, anthracene, fluorene, -(methylenebis-bistetrahydrophenyl) bismaleimide, N ,N,-(3-ethyl)-4,4-diphenylmethane bismaleimide, anthracene, Ν'_ (3,3-dimethyl)-4,4_diphenylmethane醯imine, hydrazine, hydrazine, -(3,3-diethyl)-4,4-diphenylmethane bismaleimide, hydrazine, hydrazine, -(3,3-dichloro)-4 , 4-diphenylmethane, bismaleimide, hydrazine, Ν'-isophorone, bismaleimide, hydrazine, hydrazine, -toluidine, bismaleimide, hydrazine, hydrazine, - two Phenylpropane, bismaleimide, anthracene, anthracene-naphthalene, bismaleimide, anthracene, anthracene-phenyl-p-maleimide, [Ν,Ν'-5- Oxyl-13-phenylene bismaleimide, 2,2-bis(4-(4--31 - 201107406 maleimide phenoxy)phenyl)propane, 2,2_bis ( 3-chloro-4-(4-maleimide phenoxy)phenyl)propane, 2,2-bis(3-bromo-4 _(4-maleimidophenoxy)phenyl) Propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl-4-(4-male)醯iminophenoxy)phenyl)propane, 2,2·bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane '2,2·double (3 -butyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2.bis(3-methoxy-4-(4-maleimidophenoxy)benzene Propane, I, 1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis (3-methyl-4-(4-mala) Amine phenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-bromo) -4-(4-maleimide phenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidophenoxy)pentane, 1,1,1, 3,3,3-hexafluoro-2,2-bis(4-(4-malay) Amine phenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dimethyl-4-(4-maleimide benzene) Oxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dibromo-4-(4-maleimidophenoxy) Phenyl)propane, N,N,-ethylene dimaleimide, anthracene, Ν'-hexamethylene bismaleimide, anthracene, Ν'-docamethylene double mala Imine, hydrazine, Ν'-m-xylylene bismaleimide, hydrazine, Ν'-p-xylylene bismaleimide, hydrazine, Ν'-1,3-bismethylene Cyclohexane bis-maleimide, hydrazine, Ν'-2,4·-tolyl-bis-maleimide, N,N'-2,6-tolyl-based bismaleimide, and the like. These bismaleimide compounds are not particularly limited to the above. These may be used alone or in combination of two or more. Among these bismaleimides, 2,2-bis(4-(4-male-32-201107406 imidophenoxy)phenyl)propane, N,N'-4,4 is preferred. -diphenylmethane bismaleimide, 1^1^,-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismalea An aromatic bismaleimide such as an amine. Further, in such aromatic bismaleimine, in order to obtain higher flatness, a molecular weight of 1,000 or less is preferred. In the present invention, the use ratio of the bismaleimide compound of the component (D) is preferably from 0.5 to 50 parts by mass, more preferably from 30 parts by mass, based on 100 parts by mass of the polyester of the component (A). The portion is particularly preferably 2 to 20 parts by mass. When the ratio is too small, the flattening property of the cured film obtained from the polyester composition for forming a thermosetting film is lowered. When the ratio is too large, the transmittance of the cured film may be lowered or the coating film may be rough. &lt;Solvent&gt; The polyester composition for forming a thermosetting film of the present invention is used in a state of being dissolved in a solvent. The solvent to be used in the case of dissolving the components (A) to (C) and, if necessary, the component (D) and/or other additives described later, as long as it is a solvent having such a solubility, the type and structure thereof And is particularly limited. Such a solvent is, for example, a solvent for polymerization of the component (A) or a solvent described below. For example, there are methyl cellosolve, acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, Butyl lactate, cyclohexanol, ethyl acetate 'butyl acetate, and the like. These solvents may be used singly or in combination of two or more. -33-201107406 &lt;Other Additives&gt; The polyester composition for forming a thermosetting film of the present invention may contain a surfactant, a rheology modifier, a decane coupling agent, etc. as needed, as long as the effects of the present invention are not impaired. Next, a stimulating agent such as a subsiding agent, a pigment, a dye, a storage stabilizer, an antifoaming agent, a polyphenol or a polyvalent carboxylic acid, or a hydrazine antioxidant such as an antioxidant is particularly preferably a phenol, and specific examples thereof are 2, 6- Di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, 2,4,6·tris(3',5,-di-t-butyl-4'-hydroxybenzoic acid Trimethylbenzene, pentaerythritol tetra[3-(3',5'-di-t-butyl-4-'-hydroxyphenyl)propionate], acetone bis(3,5-di-t-butyl- 4'-hydroxyphenyl)thiol, 4,4'-methylenebis(2,6-di-t-butylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl) Methyl propionate, 4,4'-thiobis(2,6-di-t-butylphenol), tris(3,5-di-t-butyl-4-hydroxybenzyl)-trimeric isocyanate , bis(3,5-di-t-butyl-4-hydroxybenzyl) sulfide, and the like. &lt;Polyester composition for forming a thermosetting film&gt; The polyester composition for forming a thermosetting film of the present invention contains a polyester of the component (A) and a ring of two or more epoxy groups of the component (B). The oxygen-containing compound or the amino group-containing carboxylic acid compound of the component (C) may optionally contain a double-maleimide compound of the component (D) and a composition of at least one of the other additives. The solution in which the solvent is dissolved is used in a large amount. The preferred embodiment of the polyester composition for forming a thermosetting film of the present invention is -34 - 201107406, as described below. [1] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 5 to 80 parts by mass of the component (C), based on 100 parts by mass of the component (A). [2] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 5 to 80 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the component (A). [3] : According to the (A) component, 100 parts by mass of the component (B) containing 3 to 50 parts by mass of the component (B), 5 to 80 parts by mass of the component (C), and the heat of the component (D) of 5 to 50 parts by mass. A polyester composition for forming a cured film. [4] : According to (A) component 100 parts by mass, '3 to 50 parts by mass of component (B), 5 to 80 parts by mass of component (C), 5.5 to 50 parts by mass of component (D) and solvent The polyester composition for forming a thermosetting film 5 The blending ratio, the sardonic method, and the like in the case where the polyester composition for forming a thermosetting film of the present invention is in a solution form are described in detail below. The ratio of the solid content in the polyester composition for forming a thermosetting film of the present invention is not particularly limited as long as the respective components are uniformly dissolved in the solvent, and is usually 1 to 80% by mass, preferably 5 to 60% by mass. More preferably 1 〇 to 50% by mass. The solid fraction refers to a solvent which is removed from the entire composition of the polyester composition for forming a thermosetting film. The preparation method of the polyester composition for forming a thermosetting film of the present invention is not particularly limited, and the preparation method may be, for example, dissolving the component (A) in a solvent, and mixing the component (B) at a specific ratio in the solution, and (C) Ingredients and (D) -35- 201107406 ingredients, a method of forming a homogeneous solution, or a method of mixing other additives as needed at an appropriate stage of the preparation method. When the polyester composition for forming a thermosetting film of the present invention is prepared, a polyester solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, in the solution of the component (A), the component (B), the component (C), the component (D) and the like are added in the same manner as described above to form a uniform solution, and a solvent can be additionally added for the purpose of concentration adjustment. In this case, when the solvent used in the formation of the polyester and the polyester composition for forming a thermosetting film are prepared, the solvents used for the concentration adjustment may be the same or different. The solution of the polyester composition for forming a thermosetting film after the preparation is preferably filtered using a filter having a pore diameter of about 2 μm or the like. &lt;Coating film, cured film, and liquid crystal alignment layer&gt; The polyester composition for forming a thermosetting film of the present invention is subjected to spin coating, flow coating, roll coating, die coating, and slit spinning Coating, inkjet coating, printing, etc., applied to a substrate (for example, a ruthenium/yttria-coated substrate, a tantalum nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, or a germanium substrate) Or a film (for example, a resin film such as a triethylenesulfonated cellulose film, a polyester film, or an acrylic film) or the like, and then preliminarily dried (prebaked) in a hot plate or an oven to form a coating film. Thereafter, the coating film is formed by heat treatment to form a film. The heat treatment conditions may be, for example, a heating temperature and a heating time which are appropriately selected from the range of a temperature of 70 ° C to 160 ° C and a time of 0.3 to 60 minutes. The heating temperature and the heating time are preferably from 80 ° C to 140 ° C and from 5 to 10 minutes. -36-201107406 Further, the film thickness of the film formed of the polyester composition for forming a thermosetting film is, for example, 0.1 to 30 μm, and can be appropriately selected in consideration of the step difference, optical properties, and electrical properties of the substrate to be used. The post-baking is generally carried out by a heating temperature selected from the range of 140 ° C to 250 ° C in the range of 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. Under the above conditions, by curing the polyester composition for forming a thermosetting film of the present invention, the step of the substrate can be sufficiently flattened, and a cured film having high transparency can be formed. The cured film thus formed can be used as a liquid crystal material alignment layer by the rubbing treatment, in other words, the function of the layer having the liquid crystal compound alignment can be generally carried out using a rotation speed of 300 to 1,000 rpm. The speed is 3~200mm/sec, and the amount of pushing is 0.1~lmm. Thereafter, it is washed with ultrasonic waves using pure water or the like to remove the residue generated by rubbing. After the phase difference material is applied onto the liquid crystal alignment layer thus formed, the phase difference material is photocured in a liquid crystal state to form a layer having optical anisotropy. As the phase difference material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the monomer or the like can be used. When the substrate forming the liquid crystal alignment layer is a film, it can be used as an optically anisotropic film. Further, the two substrates having the liquid crystal alignment layer formed as described above are bonded to each other by a spacer, and the liquid crystal alignment layers are opposed to each other, and liquid crystal is injected between the substrates to form a liquid crystal alignment. Liquid crystal display element. Therefore, the polyester composition for forming a thermosetting film of the present invention can be applied to various optical anisotropic films and liquid crystal display elements. Further, since the polyester composition for forming a thermosetting film of the present invention has at least a required level of flatness, it can be used as a display for forming a thin film transistor (TFT) type liquid crystal display element or an organic EL element. The use of a material for a cured film such as a protective film, a flattening film, or an insulating film is particularly suitable as a material for forming a color filter, a layered insulating film for a TFT liquid crystal element, and an insulating film for an organic EL element. . [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. [Abbreviation used in the examples] The meanings of the abbreviations used in the following examples are as follows. &lt;Polyester polymer raw material&gt; HBPDA: 3,3'-4,4'-dicyclohexyltetracarboxylic dianhydride THPA: 1,2,5,6-tetrahydrophthalic anhydride BPDA: biphenyltetracarboxylic acid Dihydride HBPA: hydrogenated bisphenol a -38- 201107406 BTEAC : benzyltriethylammonium chloride &lt;amino acid-containing carboxylic acid compound raw material&gt; HBPDA: 3,3'-4,4'-dicyclohexyltetradecanoic acid Dihydride CBDA: cyclohexane tetracarboxylic dianhydride THPA : 1,2,5,6-tetrahydrophthalic anhydride DA-4P : 1,3-bis(4-aminophenyl)benzene DDS : 4,4' -diaminodiphenyl milling &lt;polyimine precursor raw material&gt; CBDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride pDA: p-phenylenediamine &lt;acrylic acid copolymer raw material &gt; MAA : Methacrylic acid MMA : Methyl methacrylate HEM A : 2-hydroxyethyl methacrylate CHMI : N-cyclohexyl maleimide AIBN : azobisisobutyronitrile &lt;epoxy compound &gt; CEL : Daicel Chemical Industry Co., Ltd. Celoxide P-2021 (product name) (Compound name: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate Acid ester) -39- 201107406 &lt;Bismaleimide compound> 6?411::^_&gt;1'-(3,3-diethyl-5,5-dimethyl -4,4 methane bismaleimide 1 &lt;solvent&gt; PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether DMAc : N,N-dimethylacetamide NMP : N-A Based on the following examples, the number average molecular weight and weight average molecular weight of the polyester polymer, polyimine, and acrylic copolymer obtained by the following synthesis examples are determined by the GPC device (Shodex (Registry) Columns KF8 03 L and KF804L) were measured by stripping the elution solvent tetrahydrofuran 1 ml/min in a column (column temperature 40 ° C). Further, the following number average molecular weight (hereinafter referred to as Μη) average molecular weight (below) Mw) is expressed in terms of polystyrene. <Synthesis Example 1> By making HBPDA 12.0 g, HBPA 10.2 g, and THPA BTEAC 0.22 g in PGMEA 54.48 g, 120. Reaction 19 gives a polyester polymer solution. (solid content concentration: 3 0.0% by mass) The obtained polyester polymer had an Mn of 2,280 'Mw of 4,200. The amount of the diphenyl precursor was measured by flow rate and weight. 0.95 g 'hour, (P1) -40 - 201107406 &lt;Synthesis Example 2&gt; 14.6 g of DA-4P was dissolved in 40.68 g of DMAc, and after cooling with water, it was maintained at 23 °C. This solution was reacted with CBDA 4.90 g and THPA 7.60 g at 233⁄4 for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration: 40% by mass) (A1). &lt;Synthesis Example 3&gt; 4.97 g of DDS was dissolved in 14.95 g of DMAc, and after cooling with water, it was kept at 23 °C. This solution was reacted with CBDA 1.96 g and THPA 3.04 g at 23 ° C for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration: 40.0% by mass) (A2). &lt;Synthesis Example 4&gt;

14.61 g of DA-4P was dissolved in 41.82 g of DMAc, and after cooling with water, it was kept at 23 °C. This solution was reacted with HBPDA 7.66 g and THPA 7.60 g at 23 ° C for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration 4 0.0 mass %) (A 3 ). &lt;Synthesis Example 5&gt; By BPDA 40.0 g 'HBPA 3 5.3 g, THP A 3.3 1 g, BTEAC 0.77 g was 120 in PGMEA 175_7g. (: The reaction was carried out for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0% by mass) (P2). The obtained polyester polymer had Μη of 1,100 and Mw of 2,580. 201107406 &lt;Synthesis Example 6&gt; A polybendimide precursor solution (solid content concentration: 30.0% by mass) (P3) was obtained by reacting CBDA 17.7 g and pDA 10.2 g in NMP 66.4 g at 23 ° C for 24 hours. The resulting polyimine precursor was obtained. The body has a Μη of 5,800 'Mw of 1,2,500. &lt;Synthesis Example: MAA 10.9g, CHMI 35.3g, HEMA 25.5g, MMA 28.3g were used as monomer components, and AIBN 5g was used as a radical polymerization initiator. The polymerization reaction was carried out at a temperature of 60 ° C to 1 ° C in a solvent PGMEA 1 50 g to obtain an acrylic copolymer solution (solid content concentration: 40.0% by mass) (P4). The obtained copolymer copolymer solution had a Tn of 3,800. M w was 6 7 0 0. &lt;Example 1 to Example 6 and Comparative Example 1 to Comparative Example 4&gt; Examples 1 to 6 and Comparative Examples 1 to 4 were prepared in the compositions shown in Table 1. For each composition, planarization, solvent resistance, transmittance, and alignment are performed for each composition. -42- 201107406 [Table 1] (A) into f (B part (C) component (D solution of solvent (g) (g) (g) (g) (g) P1 CEL A1 PGME implementation Example 1 _ 20 1. 2 3. 0 9_ 4 Example 2 P1 CEL A1 PGME 20 1. 2 5. 0 10. 6 P1 CEL A1 PGME Example 3 - 20 1. 2 7. 5 12. 1 Example 4 P1 CEL A1 BMI1 PGME 20 1. 2 3. 0 0·6 11. 9 P1 CEL A2 PGME Example 5 - 20 1. 2 5. 0 10. 6 P1 CEL A3 PGME Example 6 A 20 1. 2 5. 0 10. 6 P2 CEL PGMEA Comparative Example 1 — — 20 1. 2 7. 09 P1 PGMEA Comparative Example 2 _ — 20 2. 22 P3 CEL NMP Comparative Example 3 20 1. 2 2. 97 P4 CEL PGMEA Comparative Example 4 20 1. 2 2. 80 * 卩 朽 :: polyester polymer solution, P3: polyimine precursor solution 'P4: acrylic copolymer solution [evaluation of planarization] Examples 1 to 6 and Each of the compositions of Comparative Example 1 to Comparative Example 4 was applied onto a stepped substrate (made of glass) having a height of 0.5 μm, a line width of ΙΟμηη, and a line pitch of 50 μm using a spin coater at a temperature of 1 0 0 ° C, 1 . 20 seconds in heating The pre-baked to form a coating film of a thickness of 2.8 μιη. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was heated at a temperature of 230 ° C for 30 minutes and post-baked to form a cured film having a film thickness of 2.5 μm to measure the film thickness difference between the coating film on the step substrate production line and the coating film on the gap (see FIG. 1 ). The flattening ratio was determined by the formula of the flattening ratio (DOP) = l〇〇x [l-{coating film -43-201107406 film thickness difference (μιη) / step substrate height (0.5 μιη) }]. [Evaluation of Solvent Resistance] Each of the compositions of Example 6 and Comparative Examples 1 to 4 was applied to a ruthenium wafer using a spin coater, and then heated at a temperature of 10 ° C for 120 seconds. The plate was prebaked to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked on a hot plate at a temperature of 230 ° C for 30 minutes to form a hard film having a film thickness of 2.5 μm. The cured film was immersed in PGMEA or mash for 60 seconds, and then dried at a temperature of 10 ° C for 60 seconds, and the film thickness was measured. The change in the film thickness after impregnation with PGMEA or hydrazine was evaluated as 〇, and the decrease in film thickness after immersion was evaluated as X. [Evaluation of Light Transmittance (Transparency)] Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater at a temperature of 100 ° C and 120 ° The second was pre-baked on a hot plate to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked on a hot plate at a temperature of 2 30 ° C for 30 minutes to form a cured film. The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation). -44 - 201107406 [Evaluation of the alignment property] Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied onto an ITO substrate using a spin coater at a temperature of 10 ° C, The film was pre-baked on a hot plate for 120 seconds to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked on a hot plate at a temperature of 230 ° C for 30 minutes to form a cured film.

This cured film was subjected to rubbing treatment at a rotation speed of 300 rpm, a conveyance speed of 10 mm/sec, and a pushing amount of 0.45 mm. The rubbed substrate was washed with pure water for 5 minutes. After the phase difference material composed of the liquid crystal monomer is coated on the substrate by using a spinner, it is prebaked on a hot plate at 40° C. for 30 seconds and 55° C. for 30 seconds to form a film having a film thickness of 1.1 μm. membrane. This substrate was exposed to 2000 m J under a nitrogen atmosphere. The produced substrate was rubbed with a polarizing plate to visually confirm the alignment. When the substrate was tilted at 45 degrees or not, the light transmittance was significantly changed as 〇, and the unchanged was evaluated as X.

[Evaluation of heat resistance] Each of the compositions of Example 6 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then preliminarily heated on a hot plate at a temperature of 100 ° C for 120 seconds. After baking, post-baking was performed on a hot plate at a temperature of 2 30 ° C for 30 minutes to form a cured film, and the film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the cured film was fired on a hot plate at a temperature of 2 30 ° C for 60 minutes, and the film thickness was measured again to calculate the rate of change in film thickness from the post-baking. -45- 201107406 [Evaluation results] The results of the above evaluations are shown in Table 2 below. [Table 2] Flattening ratio (%) Solvent resistance Alignment heat resistance transmittance PGMEA NMP (%) (%) Example 1 82 〇〇〇-1 93 Example 2 80 〇〇〇-1 90 Example 3 75 〇〇〇-2 88 Example 4 84 〇〇〇-2 90 Example 5 74 〇〇〇-2 89 Example 6 76 〇〇〇-3 90 Comparative Example 1 80 〇〇〇-15 96 Comparative Example 2 — XX — — — Comparative Example 3 25 〇〇〇-3 85 Comparative Example 4 88 〇〇X -0. 5 96 Examples 1 to 6 are high in flattening ratio and heat resistance, and are suitable for any of PGMEA 'NMP All have solvent resistance. In addition, both of them exhibited good alignment properties, and high transmittance (transparency) was also achieved after high-temperature firing. Further, in Comparative Example 1, the solvent resistance, the alignment property, and the flattening ratio were good, but the heat resistance was extremely low. . Further, in Comparative Example 2, a cured film was not formed. In Comparative Example 3, solvent resistance, heat resistance and alignment were good, but the flattening ratio was extremely low. In Comparative Example 4, the flatness ratio, heat resistance, solvent resistance, and transmittance were good, but the alignment property was poor. -46-201107406 When the polyester composition for forming a thermosetting film of the present invention is formed into a cured film, a glycol solvent such as propylene glycol monomethyl ether acetate can be used, and the obtained cured film can be excellent. Any of the properties of light transmittance, solvent resistance, planarization, and alignment property was good. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000- 1 No. [Fig. 1] Fig. 1 is a schematic view showing a cured film formed by coating a polyester composition for forming a thermosetting film of the present invention on a step substrate. [Fig. 2] Fig. 2 shows a conventional example. A pattern in which a liquid crystal cell (a) which forms a liquid crystal alignment film is compared with a liquid crystal cell (b) which forms a planarizing film using the polyester composition for forming a thermosetting film of the present invention. -47-

Claims (1)

201107406 VII. Application for Patent Park: 1. A polyester composition for forming a thermosetting film, which comprises (A) component, (B) component and (C) component, (A) component: tetracarboxylic dianhydride A polyester obtained by reacting with a diol compound, (B) component: an epoxy compound having two or more epoxy groups, and (C) a component obtained by reacting a diamine compound, a dicarboxylic acid anhydride, and a tetracarboxylic dianhydride. An amino group-containing carboxylic acid compound. 2. The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (A) is a polyester containing a structural unit represented by the following formula (1), [Chemical Formula 1] (In the formula, A represents a tetravalent organic group having four bonding bonds bonded to an alicyclic group or an aliphatic group, and B represents two bonding bonds bonded to an alicyclic group or an aliphatic group. Price organic basis). 3. The polyester composition for forming a thermosetting film according to the first or second aspect of the invention, wherein the component (A) is a tetracarboxylic dianhydride represented by the following formula (i) and represented by the formula (ii) Polyester obtained by the reaction of the diol compound -48 - 201107406 . (1) ΗΟ-Β-ΟΗ (ϋ) (wherein A is a tetravalent organic group having four bonding bonds bonded to an alicyclic group or an aliphatic group, and b is represented by an alicyclic group or an aliphatic group. There are two linked-bonded divalent organic groups). 4·Μ ΦPlease refer to the polyester composition for forming a thermosetting film of the second or third aspect of the patent. In the above formula (1), the lanthanoid series is represented by the following formula (Α-1) to (A-8). A group in which at least one selected from the group is selected, and b represents a group selected from at least one of the groups represented by the following formulas (B-1) to (b-5) 5. The polyester composition for forming a thermosetting film according to any one of the above-mentioned claims, wherein the weight average molecular weight of the polyester of the component (A) is 1 〇〇〇 in terms of polystyrene. 30000. 6. The polyester composition for forming a thermosetting film according to any one of claims 1 to 5, wherein the component (C) is a diamine compound 2 with respect to the tetracarboxylic dianhydride 1 Mo 201107406 ear The amine-containing carboxylic acid compound obtained by reacting the ear with a dicarboxylic anhydride 2 molar. The polyester composition for forming a thermosetting film according to any one of claims 1 to 5, wherein the component (C) is a compound represented by the following formulas (iii), (iv) and (v) Reaction-containing amine-containing residual acid compound [Chemical 5] H2n-p-nh2 (In the above formulas (iii) and (iv), the 'P and Q systems independently represent a divalent organic group, and in the formula (v), the Z system represents a tetravalent organic group). The polyester composition for forming a thermosetting film according to any one of claims 1 to 7, which contains 3 to 50 parts by mass of the component (B) based on 1 part by mass of the component (A). 5 to 80 parts by mass of the component (C). The polyester composition for forming a thermosetting film according to any one of claims 1 to 8, which further comprises a bismaleimide compound as the component (D). A polyester composition for forming a thermosetting film of the ninth aspect, which contains 0.5 to 50 parts by mass of the component (D) based on 100 parts by mass of the component (A). A cured film obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 1. The liquid crystal alignment layer is characterized in that it is obtained by using a polyester composition for forming a thermosetting film according to any one of claims 1 to 10 to 2011-07406.