TW201105737A - 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 with a dicarboxylic anhydride.

Description

[Technical Field] The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained therefrom. More specifically, the present invention relates to a polyester composition for forming a thermosetting film having a high transparency and flatness, and having liquid crystal alignment energy, high solvent resistance and heat resistance, and a cured film thereof, and The application of the cured 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, in an optical device such as a liquid crystal display element or an organic EL (electroluminescent) element, a protective film for preventing exposure of a component surface to a solvent or heat in a manufacturing step is provided. . This protective film has high adhesion to the substrate to be protected, and has high solvent resistance and performance such as transparency and heat resistance. When such a protective film is used as a protective film for a color filter used for a color liquid crystal display device or a solid-state imaging device, it is generally required to have a performance of flattening a color filter or a black matrix resin of the base substrate. That is, the performance as a planarizing film. In particular, when manufacturing a color liquid crystal display device of the STN method or the T F T method, it is necessary to perform the adhesion precision of the color filter substrate and the counter substrate very closely, and it is indispensable to uniformize the inter-substrate gap. 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, phase difference materials have been introduced into the cells of liquid crystal displays, and the cost is reduced to 0.5-201105737. In such a phase difference, a liquid crystal monomer is generally used, and after being aligned, the light is hardened. Material. In order to align this phase difference material, it is necessary to have an alignment material after the underlying film rubbing treatment. Therefore, after the liquid crystal alignment layer is formed on the coating layer of the color filter, a phase difference material can be formed (see Fig. 2(a)). When a film having a coating layer of the liquid crystal alignment layer and the color filter can be formed (see FIG. 2( b )), it is possible to obtain a material having a large cost and a large number of processes, and the like. Generally, an acrylic resin having high transparency can be used as the coating layer of the color filter. The acrylic resin of the above-mentioned type can be widely used as a glycol solvent of propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate or an ester of ethyl lactate or butyl lactate from the viewpoints of safety and workability. Solvent. Such an acrylic resin imparts heat resistance or solvent resistance by thermosetting or photocuring (Patent Documents 1 and 2). However, the conventional thermosetting or photocurable acrylic resin exhibits appropriate transparency or flattening property, but even if such a flattening film is rubbed, sufficient alignment property cannot be exhibited. Further, as the liquid crystal alignment layer, a material composed of a solvent-soluble polyimine or polylysine can be generally used. These materials are completely imidized at the time of post-baking to impart solvent resistance, and sufficient alignment property has been reported by rubbing treatment (Patent Document 3). However, when the flattening film of the color filter is viewed, there are problems such as flatness and transparency being lowered. Further, polyimine or polylysine is a solvent which is soluble in N-methyl-2-pyrrolidone or r-butyrolactone, but has low solubility in a glycol-based solvent or an ester-based solvent. Difficult to apply to the flat film production line. -6- 201105737 [Summary of the Invention] [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned problems, and the object to be solved is to provide a material which is formed after the formation of a cured film. High solubility, liquid crystal alignment, heat resistance, high transparency, and high flatness, and when the cured film is formed, it is soluble in the glycol produced on the production line of the flattening film of the color filter. It is a material of a solvent or a lactic acid ester solvent. [Means for Solving the Problem] The present inventors have found out the present invention by focusing on the above-mentioned problems and focusing on the results. In other words, the first aspect relates to a polyester composition for forming a thermosetting film comprising (A) component, (B) component, and (C) component; (A) component: tetracarboxylic dianhydride and Polyester obtained by the reaction of a diol compound, component (B): an epoxy compound having two or more epoxy groups, and (C) component: an amine group-containing carboxylic acid obtained by reacting a diamine compound with a dicarboxylic anhydride Compound. The second aspect of the invention relates to a polyester composition for forming a thermosetting film according to the first aspect, wherein the component (A) contains a polyester having a structural unit represented by the following formula (1); 201105737 [Chemical Formula 1]

(wherein, A represents a tetravalent organic group to which four bonding bonds have been bonded on an alicyclic group or an aliphatic group, and B represents two bonding bonds on an alicyclic group or an aliphatic group. A 2 valent organic group). The third aspect is a polyester composition for forming a thermosetting film which is contained in the first aspect or the second aspect, wherein the component (A) is a tetracarboxylic dianhydride represented by the following formula (i). a polyester obtained by reacting a diol compound represented by the formula (ii); [Chemical 2] Ο Ο〇 «〇 (i) HO-B-OH (ii) (wherein, A is represented by an alicyclic group or an aliphatic group A 4-valent organic group to which four bonding bonds have been bonded, and B represents a divalent organic group to which two bonding bonds have been bonded to an alicyclic group or an aliphatic group. The fourth aspect is the polyester composition for forming a thermosetting film according to the second or third aspect, wherein in the above formula (1), A is represented by the following formula (A-1) to formula (A-8). At least one selected from the group shown, and B represents at least one selected from the group represented by the following formula (B-1) to formula (B-5). -8- 201105737 【化3】 » W V® (Α·1) (Α-2) (Α-3) (Α-4) (Α-5) (Α-6)

(Α-7) (Α-8) 【化4】

(Β-4) (Β*5) χ>ΕΡ ^ (Β_1) ( Β·2 > (Β-3) The fifth aspect relates to the formation of a thermosetting film for use in any one of the first to fourth aspects In the ester composition, the weight average molecular weight of the polyester of the (Α) component is from 1 000 to 30,000 in terms of polystyrene. The sixth aspect of the invention relates to the thermosetting film forming composition according to any one of the first to fifth aspects The ester composition, wherein the component (C) is an amine group-containing carboxylic acid compound obtained by reacting a diamine compound 1 molar with a dicarboxylic anhydride of 1.7 to 2 mol. The seventh aspect is related to the first to sixth aspects. A polyester composition for forming a thermosetting film, which contains 3 to 50 parts by mass of the (Β) component and 3 to 50 parts by mass of the component (C) based on 100 parts by mass of the (Α) component. In view of the above, the polyester composition for forming a thermosetting film of the above-mentioned item No. 7 to the above-mentioned item further contains a bismaleimide compound as the component (D). The ninth point is about the eighth aspect. The polyester composition for forming a thermosetting film, which contains (5) parts by mass of the component (D) based on 1 part by mass of the component (A). -9- 20110573 The tenth 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 ninth aspects. The eleventh aspect relates to a liquid crystal alignment layer which is used. The polyester composition for forming a thermosetting film according to any one of the first to ninth aspects of the present invention. [Effect of the Invention] The polyester composition for forming a thermosetting film of the present invention has high flatness and high transparency. In addition to high solvent resistance and high heat resistance, it can form a cured film having liquid crystal alignment energy, so it can be used as a material for forming a liquid crystal alignment film or a planarization film. In the coating layer of the liquid crystal alignment film and the color filter, the "liquid crystal alignment layer" having both characteristics can be formed at one time, and the manufacturing process can be simplified and the number of processes can be reduced, etc. Further, the present invention The polyester composition for forming a thermosetting film is soluble in a glycol solvent and a lactic acid ester solvent, and therefore can be suitably used in a production line for using a flattening film mainly composed of such a solvent. In the cured film of the acrylic resin and the polyimine which have been proposed in the past, the flatness, transparency, alignment, etc. which are obtained by the liquid crystal alignment film or the planarizing film cannot be sufficiently satisfied. In addition, it has been proposed that polyester is used as an alignment material for a liquid crystal display element (see Japanese Patent Laid-Open No. Hei 5-158055, No. 2002-229039), but none of them has any heat. The curable property, the formed film -10- 201105737 is inferior in solvent resistance. The present invention is characterized in that it is characterized by using a thermosetting polyester, that is, a polyester containing (A) component, The epoxy resin compound having two or more epoxy groups and (C) the carboxylic acid compound having an amine group is composed of a polyester for forming a thermosetting film: Step (A) component, (B) component, and (C) Ingredients: A thermosetting/polyester composition containing a bismaleimide compound as the component (D). Hereinafter, the contents of each component will be described. [(A) component] The polyester of the component (A) preferably contains a polyester having a unit of the following formula (1), and more preferably a polyester having a structure represented by the formula (1). [Chem. 5] can improve the content of the ingredients. Further, it can also be constructed by the structure of the film formation.

HOOCwC〇OH 0—C-A—C-O-B II Ο 〇

(1) In the above formula, 'Α denotes a 4-valent organic group to which a 4-bond has been bonded to an alicyclic group or an aliphatic group. 'B indicates that two bonding bonds are bonded to an alicyclic group or a dragon. A divalent organic group. The above A is preferably a group represented by the following formula (1A1), formula (1A2) or 〕). Bonded aliphatic group i (1A3 -11- 201105737 [Chem. 6] XX >1-< (1A1) (1A2) (1A3) wherein A1 represents a cyclic saturated hydrocarbon group, preferably a carbon atom The cyclic saturated hydrocarbon group of 4 to 8 is more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the A1 group may be independently substituted with an aliphatic group, and In addition, two substituents may be bonded to each other to form a 4 to 6 membered ring. Here, the aliphatic group of the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably a carbon number. An aliphatic group of 1 to 3, wherein 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, or a partially or wholly hydrogenated condensed polycyclic hydrocarbon group. R1 represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted by a fluorine atom. It is preferably a single bond, a carbonyl group or 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. R2 represents a carbon number of 1 to 8 The saturated hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. A preferred specific example of A of the tetravalent organic group in the formula (1) In the following formula (A-1) to formula (A-8), in the group represented by the following (A-1) to (A-8), A is particularly preferably of the formula (A-). 1) or (A-2) selected base. -12- 201105737 【化7】 XX w (Α·1 ) (Α-2) (Α-3) (A·4) (A-5) (Α- β) In the above formula (1), 'B' represents a divalent organic group to which two bonding bonds are bonded to an alicyclic group or an aliphatic group, and is preferably a formula (1B1) or a formula (1B2) A group of R4_B1+R3_B1 荃R5-R6-B2-R7- (1B1) (1B2) wherein B1 represents a cyclic saturated hydrocarbon group, preferably a ring having 4 to 8 carbon atoms. The saturated hydrocarbon group preferably represents 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. Here, the fat of the substituent The family group is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. In the ring, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantyl group, or a hydrogenated condensed polycyclic hydrocarbon group. B 2 represents a benzene group. In the formula, R 3 represents a single bond, a carbonyl 'ether. a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon having 1 to 8 carbon atoms substituted by a fluorine atom, preferably a single bond, a carbonyl group, an ether group or 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. R4 and R5 each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and preferably represent a single bond or an alkylene group having 1 to 3 carbon atoms. R6 and R7 each independently represent an alkylene group having 1 to 5 carbon atoms, and preferably represent an alkylene group having 1 to 3 carbon atoms. Again k means 〇 or 1. A preferred specific example of B of the divalent organic group in the formula (1) is shown in the following formula (B-1) to formula (B-5). In the group represented by the following formula (B-1) to (B-5), B is particularly preferably a group selected from the formula (B-1) or (B-4). 【化9】

(B-3)

(B-5) (B-4) The polyester of the component (A) is preferably a structural unit represented by the formula (1), and A preferably contains at least one selected from the group consisting of the formula (1A1) to the formula (1A3). The structure in the group formed by the base of the formula may have a structure other than the group represented by the formula (1A1) to the formula (1A3). In the meantime, the structure of the polyester is not particularly limited, and it is preferably at least one selected from the group consisting of the groups represented by the following formulas (1A4) to (1A5).

201105737 In the above formula, R8, R9 and R1Q 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 saturated hydrocarbon group having 1 to 8 carbon atoms substituted by a fluorine atom. It 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 saturated hydrocarbon group having 1 to 5 carbon atoms which is substituted by a fluorine atom. In particular, R8 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 represents an ether group and a carbon number. a saturated hydrocarbon group of 1 to 5 or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted by a fluorine atom, preferably R1() represents 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 1 to 5 carbon atoms. Also h represents 0 or 1. Preferred specific examples of the above formula (1 A4 ) to formula (1 A5 ) are shown in the following formulas (al) to (a7). [1 1]

^CC (a1 &gt; (a2) (a3) (a4) (a6) (a5) (a7) In the polyester of the component (A) used in the present invention, the structure represented by the above formula (1) In the unit, A preferably contains at least -15-201105737 6 〇 mol% or more of at least one selected from the group consisting of the groups represented by the formulas (1A1) to (1A3). The weight average molecular weight of the ester is preferably from 1 000 to 3 0000 ', more preferably from 1,500 to 10,0 Å. 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 are lowered. When the content exceeds the above range, the planarization property may be lowered. <Production Method of Component (A)&gt; In the present invention, the polyester of the component (A) may be, for example, tetracarboxylic dianhydride and More specifically, a tetracarboxylic dianhydride (hereinafter, also referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i), and a formula (ii) The diol compound (hereinafter referred to as a diol component) of the diol compound shown is obtained by reacting. [Chemical 1 2]

(1) HO-B-OH (ii) The 'A and B systems in the above formula are the same as defined in the above formula (1), and the preferred embodiment is also 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 singly or in combination of two or more kinds. In the polyester component of the above (A) component, not only the tetracarboxylic dianhydride represented by the above formula (i) but also a tetracarboxylic dianhydride other than the above-mentioned formula (i) can be used (hereinafter also referred to as other Acid dianhydride). In the meantime, the other acid dianhydride-16-201105737 is not particularly limited as long as the effects of the present invention are not impaired. The tetracarboxylic dianhydride represented by the following formula (i2) is preferred. [化1 3] Ο 〇

Here, the structure of the above formula (i2) is at least one selected from the group consisting of the formulas represented by the formula (1A4) and the formula (1A5) defined in the above formula (1), R8 and R9. Further, R1G and h are also as defined above, and preferred specific examples of the formula (1A4) and the formula (1A5) are also represented by the above formula (al) to (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. In the polyester of the above component (A), the ratio of the total amount 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), that is, The total number of moles of the alcohol compound) / (the total number of moles of the tetracarboxylic dianhydride compound) is preferably from 0.5 to 1.5. In general, the polycondensation reaction is similar. 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 preferably such that the stability of the preservation stability is lowered. Anhydride end. 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. -17-201105737 Further, when the diol component is excessively used, the terminal is easily formed. At this time, the terminal hydroxyl group is reacted with a carboxylic acid anhydride to form a hydroxyl group by an acid anhydride. Examples of such a carboxylic acid anhydride include phthalic anhydride, trimellitic acid, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride 'tetrahydride' I, 2-cyclohexanedicarboxylic anhydride, 4-methyl- I,2-cyclohexanedicarboxy-4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-based carboxylic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, double ring [2ene-2,3-dicarboxylic anhydride and the like. In the production of the polyester of the above component (A), the reaction temperature of the acid component and the second component may be 50 to 20 (TC, preferably 80 to 170 ° C. For example, the reaction temperature may be 100 to 140 ° C, the reaction The polyester is obtained at time 2. Further, the reaction temperature at the time of protecting the terminal hydroxyl group with an acid anhydride is selected to be any temperature of ° C, preferably 80 to 17 ° C. The reaction between the above acid component and the diol component is generally in a solvent. The solvent which can be used is not particularly limited as long as it does not contain a functional group such as a hydroxyl group or an amine group and an acid, and examples thereof include N,N-diamine and N,N-dimethylacetamide. N-methyl-2-pyrrolidone, pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide, tetramethyl, dimethyl milling, hexamethyl argon, m-cresol, butyrolactone, Cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-glyoxime propylene glycol acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate 3-methoxypropionate , 3-methoxypropionic acid ethyl ester, 2-methoxy group is a hydroxyl-terminated terminal anhydride anhydride hydroquinic acid anhydride, -2,3-di-2.2] octanol component temperature ~ 4 8 /J\ 50~ 200. Reaction methyl N-vinyl urea cyclohexanol monomethyl ketone, propionic acid B · 18 · 201105737 ester, 3-ethoxy propionate ethyl ester, 2-ethoxy propionate ethyl ester, etc. The solvent may be used singly or in combination, but it is more preferably propylene glycol monomethyl ether acetate from the viewpoint of safety and the production line of the color filter coating agent. Further, it may be The solvent of the solvent polyester may be used in combination with the solvent in the range in which the polyester formed by the polymerization reaction does not precipitate. Further, the above-mentioned acid components (formula (i) and formula (i2)) and the diol component ( A catalyst may be used in the reaction of the formula (ii)). Specific examples of the catalyst used in the polymerization of the polyester include, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and chlorine. Benzyltriethylammonium, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetrabromide bromide a quaternary ammonium salt such as ammonium amide, tetrapropylammonium chloride or tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyl chloride 4-phosphorus salt, such as a phosphonium phosphate, a benzyltriphenylphosphonium bromide, an ethyltriphenylphosphoric acid chloride, or an ethyltriphenylphosphonium bromide gun. The polyester solution of the component can be directly used in the preparation of the polyester composition for forming a thermosetting film. Further, the obtained polyester is weak in water, methanol, ethanol, diethyl ether, hexane, or the like. After the solvent is precipitated and recovered, it may be used. &lt;(B) Component&gt; I S1 The epoxy compound having two or more epoxy groups of the component (B) of the present invention, for example, three (2, 3) _Epoxypropyl)trimeric isocyanate, -19- 201105737 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, Gan Alcohol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxy) Propyl)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate An acid ester, a trimethylolethane triglycidyl ether, a bisphenol-A-diglycidyl ether, and a pentaerythritol polyglycidyl ether. Further, a compound of a commercially available product can also be used from the viewpoint of easy availability. Specific examples (trade names) are listed below, but are not limited thereto: epoxy groups having an amine group such as YH-434 and YH434L (manufactured by Tosho Kasei Co., Ltd.); Epolead GT-401, Epolead GT-403 Ερο 1 ead GT-301, Epolead GT-3 02, Celoxide 202 1, Celoxide 3000 (made by Daicel Chemical Industry Co., Ltd.), epoxy resin having a cyclohexene oxide structure; Epikote 1001, Epikote 1 002, Epikote 1 0 0 3, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, oiled Shell Epoxy (now Japan Epoxy Resin)), etc. ; Epikote 807 (oiled Shell Epoxy (now Japan Epoxy Resin)) and other bisphenol F-type epoxy resin; Epikote 152, Epikotel54 (above, oiled Shell Epoxy (share) (now Japan Epoxy Resin () system)), EPPN 20 1, EPPN 202 (above, Nippon Chemical Co., Ltd.), etc. Phenolic novolac type epoxy resin: EOCN-102, EOCN-103S, EOCN-104S 'EOCN- 1 020, EOCN-1 025, EOCN-1027 (on -20-201105737, Japanese chemical medicine ( )), Epikotel 80S75 (oiled Shell Epoxy (now Japan Epoxy Resin)), etc. between the enamel-type epoxy resin; Denacol EX-252 (Nagase Chemtex) CY 1 75 ' CY 1 77, CY 1 79, Araldite CY-1 82, Araldite CY-192, Araldite CY-184 (above, manufactured by CIBA-GEIGY AG), Epiclon 200, Epiclon 400 (above, Dainippon Ink Chemical Industry) (shares) (current DIC (share)) system, Epikote871, Epikote872 (above, oiled Shell Epoxy (shares) (now Japan Epoxy Resin (share))), ED-566 1, ED-5662 (above, Celanese Epoxy epoxy resin such as Coating Co., Ltd.; 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-32 1 (manufactured by Nagase Chemtex Co., Ltd.). Further, as the compound having at least two epoxy groups, a polymer having an epoxy group can be used. 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. As an example, for example, polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate, and styrene and 2-hydroxyethyl group can be mentioned. An addition polymerizable polymer such as a acrylate copolymer or a polycondensation polymer such as an epoxy novolac. -21-201105737 Alternatively, the above epoxy group-containing polymer may be reacted with a compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl p-toluenesulfonate. Manufacturing. The weight average molecular weight of such a polymer is, for example, 300 to 200,000. The epoxy compound having at least two epoxy groups may be used singly or in combination of two or more kinds. The content of the epoxy group having two or more epoxy groups of the component (B) in the polyester composition for forming a thermosetting film of the present invention is preferably 3 parts by mass based on the mass of the polyester of the component (a). 50 parts by mass, more preferably 5 to 40 parts by mass, particularly preferably 1 to 30 parts by mass. When the ratio is too small, the solvent resistance and heat resistance of the cured film obtained from the polyester composition for thermosetting film formation are lowered, and when it is too large, the solvent resistance may be lowered or the storage stability may be lowered. (C) Component&gt; The component (C) is an amine group-containing carboxylic acid compound obtained by reacting a diamine compound with a dicarboxylic acid dianhydride. The details are obtained by reacting the diamine compound 1 mol represented by the following formula (iii) with the diacetyl dianhydride represented by the formula (iv) by 1.7 to 2 mol, preferably 1.8 to 2 mol. An amine group-containing carboxylic acid compound.

[Chem. 1 4] H2N-P-NH2 (iii) -22- 201105737 The organic group in formula (iii) and formula (iv). In the case where the 'P and Q are each independently a divalent diamine compound and reacted with a dicarboxylic acid represented by the formula (2) and thus represented by the above formula (iii), 俾Compounds are available. 【化1 5】 Ο Ο HOOC,

Q NH P,

NH

Q /C〇〇h (2) In the formula (2), the 'P and Q systems are synonymous with the above formula (iH) and the formula (i〇). In the present invention, the 'diamine compound and the dicarboxylic anhydride system may be Only one type may be used, and a plurality of types may be used. Therefore, the amine group-containing carboxylic acid compound of the component (C) of the present invention may be used alone or in combination with a compound of the formula (2). The P and Q systems are preferably a divalent organic group each having a ring structure independently. Here, the ring structure may, for example, be a benzene ring, an alicyclic ring or a condensed polycyclic hydrocarbon. In the formula (iii), P has The ring structure is preferably a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms. Therefore, specific examples of the diamine compound having such a ring structure include the following : p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,4-dimethyl-1,3- Diamino-23- 201105737 Benzene, 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-diaminobenzoic acid, N,N-diallyl-2,4-diaminoaniline, N,N-diallyl-2,5 -diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 2-(3-aminophenyl)ethyl Amine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamino Biphenyl, 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'-diaminobiphenyl, 2,2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3, 4'-Diaminodiphenylmethane '4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, N-methyl (4,4'-di Aminodiphenyl)amine, N-methyl(3,3'-diaminodiphenyl)amine, N-methyl(3,4'-diaminodiphenyl)amine, 4,4' -diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzimidamide, 1, 2-bis(4-aminophenyl)ethane, 1,2-bis(3-aminophenyl)ethane, 4,4'-diaminotolane (diaminotolane), 1,3-double (4-Aminophenyl)propane, I,3·bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-amino group Phenyl)propane, 2,2-bis(3-amino-4--24-201105737 methylphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2- Bis(3-aminophenyl)hexafluoropropane, 2,2-bis(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)hexyl Alkane, 1,7-double (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, double (4-Aminophenyl)propane diester, bis(4-aminophenyl)butane dicarboxylate, bis(4-aminophenyl)pentane dicarboxylate, bis(4-aminobenzene) Hexanedicarboxylate, bis(4-aminophenyl)heptanedioate, bis(4-aminophenyl)octanedioate, bis(4-aminophenyl)decane Acid ester, bis(4-aminophenyl)decane diester, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1, 4-bis(4-aminophenoxy)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)isodecanoate, I,4·phenylexyl bis[(4-aminophenyl)methanone], 1 4-phenylexyl bis[(3-aminophenyl)methanone], 1,3-phenylexyl bis[(4-aminophenyl)methanone], 1,3-benzeneexyl bis[( 3-aminophenyl)methanone], 1,4-phenylexyl bis(4-aminobenzoate), 1,4-phenylexyl bis(3-aminobenzoate), 1 , 3-phenylexyl bis(4-aminobenzoate), 1,3-phenylexyl bis(3-aminobenzoate), N,N'- (1,4-phenylene) Bis(4-aminobenzophthalamide), hydrazine, Ν'-(1,3-phenylexyl) bis(4-amino-25-201105737 benzoguanamine), N,N'-(1 , 4·Benzene) bis(3-aminobenzo, 1^ less '-(1,3-phenylexyl) bis(3-aminobenzophthalamide), bisphenyl) Amine, bis(3-aminophenyl)-p-amine, aminophenyl)isodecylamine, bis(3-aminophenyl)isoindole [4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-oxy)phenyl]hexafluoropropane, 4,4'-bis(4-aminophenoxy)anthracene, 2,6-di Aminopyridine, 2,4-diamine pyridine, 2,4-diamino-1,3,2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, amine II Benzofuran, 2,6-diamine taste Azole, 2,7-diaminopurine oxime carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2 4-aminophenyl)-1 , 3,4-oxadiazole, 1,4-diaminocyclohexane, 1-cyclohexane, bis(4-aminocyclohexyl)methane, bis(4-amino.cyclohexyl), etc. . Further, in the above formula (iv), the ring structure of Q is preferably an alicyclic ring having a benzene atom number of 4 to 8, and a condensed polycyclic ring having 7 to 16 carbon atoms. Preferably, Q is a benzene ring and a carbon number is 4-8. Alicyclic ring, number of carbon atoms: Condensed polycyclic hydrocarbon. Specific examples of the dicarboxylic acid anhydride having such a ring structure include an acid anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrazine methyl-5-norbornyl-2,3-diresin anhydride, and clothes. Kang anhydride, tetraanhydride, and the like. In the production of the compound of the above (C) component, the reaction temperature of the diamined di-residual acid anhydride may be selected from 5 to 8 (rc, preferably 1 Torr to 5 Torr). The amine amine (4-amine double (4) -c ' 2,2-aminophenyldiphenyl, 5-triazine 3,6-dibu 3,6-,5-bis(,3-diamine-3-methylcyclo, hydrocarbon). For example, phthalic anhydride, hydroquinone hydride, and any of them -26-201105737 The above reaction is generally carried out in a solvent, and it is possible to use a functional group which does not contain a hydroxyl group or an amine group and reacts with an acid anhydride. There is no particular limitation, and examples thereof include hydrazine, hydrazine-dimethylformamide, N,N-diamine, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, caprolactam, dimethylimidazole. , dimethyl hydrazine, tetramethyl urethanyl maple, hexamethyl hydrazine, m-cresol, r-butyrolactone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol Monoformate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl propyl propionate, ethyl 3-methoxypropionate, ethyl ethoxylate 2-methoxypropionate Ethyl propionate, ethyl 2-ethoxypropionate, methyl cellosolve, ethyl Fibril acetate, methyl cellosolve, ethyl cellosolve, fiber, propylene glycol monomethyl ether, propylene glycol propyl ether, butyl acetate, cyclohexanol, ethyl acetate, butyl acetate Ethyl lactate, ester, etc. These solvents may be used singly or in combination, but from the perspective of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate dimethyl acetamide, N-A Further, even if the carboxylic acid compound containing an amine group is not dissolved, the compound formed by the polymerization reaction does not precipitate, and is used in combination with the above solvent. The content of the polyester composition for forming a thermosetting film is preferably 100 parts by mass or more based on 100 parts by mass of the polyester of the component (A), and is preferably from 5 to 40 parts by mass. The alignment of the cured film obtained by the ester composition will be reduced. The solvent is only I, and methyl ethyl N-methyl, dimethyl, cyclopentyl ether ethyl 2-methoxy decyl ester, 3-acetate butyl solution The solvent of lactic acid lactic acid and N, N- may be mixed (C) into a 3~50 type I hardened film. Further, S 1 -27-201105737, when the ratio is too large, the transmittance is lowered or the flatness is lowered. &lt;(D) component&gt; In the present invention, the component (D) may also contain the following formula (3). The bismaleimide compound shown in the formula. The bismaleimide compound of the component (D) is further effective in improving the planarization property.

In the formula, Y is an organic group selected from the group consisting of an aliphatic group, an organic group containing a group of an aliphatic group and an aromatic group having a cyclic structure, or a combination of a plurality of organic groups selected from the group. Further, Y may also contain a combination of an ester bond, an ether bond, a guanamine bond, a urethane or the like. Such a bismaleimide compound may, for example, be N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl-5,5 -Dimethyl)-4,4-diphenyl-methane bismaleimide, n,N'-4,4-diphenylmethane bismaleimide, 3,3-diphenyl mill Bismaleimide, 4,4-diphenylfluorene, bismaleimide, N,N,-p-benzophenone, bismaleimide, n,N,-diphenylethane Maleic imine, N,N,-diphenyl ether bismaleimide, N,N'-(methylenebis-bistetrahydrophenyl) bismaleimide, n,N, -(3-ethyl)-4,4-diphenylmethane bismaleimide, n,N,-(3,3-dimethyl)-4,4-diphenylmethane bismale Imine, :^1^'-(3,3-diethyl)- -28- 201105737 4.4- Diphenylmethane bismaleimide, N,N'-(3,3-dichloro)- 4,4-diphenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N,-dimethyl-p-diaminobenzoicinide , N,N'-diphenylpropane, bismaleimide, N,N'-naphthalene, bismaleimide, N,N'-m-phenylexene, Bismale Amine, N,N,-5-methoxy-1,3-benzene-extended bismaleimide '2,2-bis(4-(4-maleimidophenoxy)phenyl) Propane, 2,2-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-mala) Amine phenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl -4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane , 2,2-bis(3-butyl_4-(4_maleimide phenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-(4-male)醯iminophenoxy)phenyl)propane, anthracene, 1·bis(4·(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-methyl- 4 - (4-maleimide phenoxy)phenyl) phenyl, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)ethane, 1 , 1-bis(3-bromo-4-(maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidophenoxy)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-maleimide) Oxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3.5-dimethyl-4-(4-maleimidophenoxy)benzene Propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dibromo-4-(4-maleimidophenoxy)phenyl)propane , N,M,-Ethylene dimaleimide, anthracene, Ν'-hexamethylene bismaleimide, anthracene, Ν'-docamethylene bis-maleimide, hydrazine ,Ν'-m-xylene-extension, bismaleimide, ν, Ν,-p-xylene, bis--29-201105737, maleimine, N, N'-1,3-bismethylene Cyclohexane Bismaleimide, ratio: ^ 2,4-toluene extended bismaleimide, :^,:1^-2,6-toluene extended bismaleimide. These bismaleimide compounds are not particularly limited to those described above. These may be used alone or in combination of two or more components. Among these bismaleimides, 2,2-bis(4-(4·maleimidephenoxy)phenyl)propane, N,N'-4,4-diphenyl is preferred. Aroma of methane bismaleimide, N,N'-(3,3·diethyl-5,5-dimethyl)-4,4-diphenyl-methyl sulphate The family is a double horse. Further, in such aromatic bismaleimine, in order to obtain higher flatness, it is preferably one having a molecular weight of 1,000 or less. 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 1 to 30, per part by mass of the polyester of the component (A). The mass part is particularly preferably 2 to 20 parts by mass. When the ratio is too small, the flatness of the cured film obtained from the polyester composition for forming a thermosetting film is lowered, and when it 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 usually used in the form of a solution dissolved in a solvent. The solvent used at this time dissolves the components (A) to (C), the component (D), and/or other additives described later, and is a solvent having such a solubility, and the type and structure thereof. Specially limited. Such a solvent may, for example, be a solvent used for the polymerization of the component (A), 30-201105737 or a solvent described below. For example, methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, lactate B Ester, butyl lactate, cyclohexanol, ethyl acetate, butyl acetate, and the like. These solvents may be used alone or in combination of two or more. <Other additives> Further, the polyester composition for forming a thermosetting film of the present invention may be used as needed as long as the effects of the present invention are not impaired. A solution accelerator, a pigment, a dye, a storage stabilizer, an antifoaming agent, a dissolution promoter such as a polyvalent phenol or a polyvalent carboxylic acid, an antioxidant, and the like are contained in a surfactant, a rheology modifier, a decane coupling agent, or the like. The antioxidant is particularly preferably a phenol, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-phenol, and 2,4,6-three. (3',5'-di-tert-butyl-4'-hydroxybenzyl)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) , methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoate, 4,4'-thiobis(2,6-di-t-butylphenol), three (3,5) -Di-tert-butyl-4-hydroxybenzyl)trimeric isocyanate bis(3,5-di-t-butyl-4-cyclobenzyl) sulfide. &lt;Polyester composition for forming a thermosetting film&gt; -31-201105737 The polyester composition for forming a thermosetting film of the present invention contains the polyester of the component (A) and the component (B) having two or more epoxy resins. The epoxy group-containing compound and the amine group-containing carboxylic acid compound of the component (C) may contain one or more of the other compounds, and may further contain the bismaleimide compound of the component (D). Then, it is often used as a solution in which it is dissolved in a solvent. Among them, preferred examples of the polyester composition for forming a thermosetting film of the present invention are as follows. [1] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 3 to 50 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), 3 to 5 parts by mass of the component (C), and a solvent, based on 100 parts by mass of the component (A). [3]: According to 100 parts by mass of the component (A), it contains 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 0.5 to 50 parts by mass of the component (D). A polyester composition for film formation. [4]: According to 100 parts by mass of the component (A), it contains 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 〇5 to 50 parts by mass of the component (D). A polyester composition for forming a thermosetting film of a solvent. The blending ratio, the preparation method, and the like in the case where the polyester composition for forming a thermosetting film of the present invention is in the form of a solution 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 each component is uniformly dissolved in a solvent - 32-201105737 but 1 to 80% by mass, preferably 5 ~60% by mass, more preferably 10%. Here, the solid form is a person who removes a solvent from a polyester formed of a thermosetting film. The preparation of the polyester composition for forming a thermosetting film of the present invention is particularly limited. However, the preparation method may be, for example, dissolving the component (A), and mixing the component (B) at a specific ratio in the solution, ((further (D) a component, a method of forming a uniform solution, or a further addition method as needed in an appropriate stage. When the polyester composition for forming a thermosetting film of the present invention is adjusted, it can be directly used in a solvent. When the polyester obtained by the polymerization reaction is dissolved in the solution of the component (A) in the same manner as described above, the Ϊ (C) component, the component (D), and the like are formed to form a uniform solution, and further added for the purpose. In this case, the solvent used in the polymerization process and the solvent used for the concentration adjustment of the polyester for forming a thermosetting film may be the same, or may be a polyester for forming a thermosetting film which is prepared in succession. The composition 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 based on a base/two oxygen矽 coated substrate, tantalum nitride substrate, metal, example, coated substrate such as chrome, glass substrate 'quartz substrate, total composition of IT 〜 ～50% by mass I, no solvent solution), this preparation agent In the case of mixing, the liquid is liquid. At this time, the composition of the bismuth component and the product of the concentration-adjusting ester are different, and then the plate is used (for example, a 锟' molybdenum substrate, etc.) -33-201105737 or a film (for example, three-ethyl A spin coating, a vertical coating, a light coating, a die coating, a spin coating of a die slit, an inkjet, etc., a resin film such as a mercapto cellulose film, a polyester film, or an acrylic film) Coating is carried out by coating, printing, etc., and then pre-drying (prebaking) is performed by a hot plate or an oven, etc., and a coating film can be formed by 俾. Then, this coating film is heat-processed, and a film can be formed by 俾. The heat treatment conditions may be, for example, a heating temperature and a heating time appropriately selected from a temperature of 70 ° C to 16 (TC, time 0.3 to 60 minutes. The heating temperature and heating time are preferably 80 ° C to 140 ° C. , 0.5~10 minutes 〇 again, by hot hard The film thickness of the film formed of the polyester composition for film formation is, for example, 0.1 to 3 μm, which can be appropriately selected in consideration of the step difference, optical properties, and electrical properties of the substrate to be used. Post-baking is generally performed by a temperature of 40 The heating temperature selected in the range of °C ~ 2 5 〇 °C is 5 to 30 minutes on the hot plate, and the method is carried out in the oven for 30 to 90 minutes. When the polyester composition for forming a thermosetting film of the present invention is cured, the step of the substrate can be sufficiently flattened to form a cured film having high transparency. The hardened film formed by the method is subjected to rubbing treatment. It can exhibit a layer function as a liquid crystal material alignment layer and even a liquid crystal compound. The conditions of the rubbing treatment can generally be as follows: a rotation speed of 300 to 1000 rpm, a conveying speed of 3 to 200 mm/sec, and a pushing amount. -34- 201105737 Thereafter, it is washed with ultrasonic waves using pure water or the like to remove the residue generated by the rubbing. After coating the phase difference material on the liquid crystal alignment layer formed in this manner, the phase difference material is formed into a liquid crystal state and photohardened, whereby a layer having optical anisotropy can be formed. As the phase difference material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same can be used. Then, when the substrate on which the liquid crystal alignment layer is formed is a film, it can be used as an optical anisotropic film. Further, the two substrates having the liquid crystal alignment layer formed in this manner are bonded to each other via a spacer and the liquid crystal alignment layer is opposed to each other, and then liquid crystal is injected between the substrates to form a liquid crystal alignment liquid crystal display. element. Therefore, various polyester anisotropic films and liquid crystal display elements can be suitably used as the polyester composition for forming a thermosetting film of the present invention. Further, since the polyester composition for forming a thermosetting film of the present invention has at least an indispensable level of flatness, it can be used as various types of displays for forming a thin film transistor (TFT) type liquid crystal display element, an organic EL element, and the like. The material of the cured film such as a protective film, a flattening film, or an insulating film is particularly suitable as a material for forming a coating layer of a color filter, an interlayer insulating film of a TFT-type liquid crystal element, or an insulating film of 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 raw material&gt; HBPDA: 3,3,-4,4'-dicyclohexyltetracarboxylic dianhydride BPDA: biphenyltetracarboxylic dianhydride BPADA: 4,4'-(4,4'-iso Propylenediphenoxy)bisphthalic anhydride

HBPA: hydrogenated bisphenol A THPA : 1,2,5,6-tetrahydrophthalic anhydride &lt;polyester polymerization catalyst&gt; BTEAC : benzyltriethylammonium chloride &lt;amino acid-containing carboxylic acid compound raw material &gt DA-4P : 1,3-bis(4-aminophenyl)benzene DA-1M : 4,4'-bis(4-aminophenoxy)diphenylphosphonium TA: trimellitic anhydride DDM: 4,4'-Diaminodiphenylmethane&lt;Polyimide precursor raw material&gt; CBDA: Cyclohexanetetracarboxylic dianhydride PDA: p-phenylenediamine-36- 201105737 &lt;Acrylic copolymer raw material &gt; MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: azobisisobutyronitrile &lt;epoxy compound&gt CEL: Dai cel Chemical Industry (Celoxide P-2021 (product name) (Compound name: 3,4-epoxycyclohexenylmethyl-3,, 4'-epoxycyclohexene carboxylate Acid ester) &lt;Bismaleimide compound> BM11: N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismale醯imine &lt;solvent&gt; PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether DMAc: Ν, Ν - II The number average molecular weight and weight average molecular weight of the polyester, the polyimide precursor and the acrylic copolymer obtained by the following synthesis example ' Ν 甲基 -methyl-2-pyrrolidone are LS } -37 - 201105737 GSP unit (Shodex (registered trademark) column KF803 L and KF804L) manufactured by Japan Separation Co., Ltd., so that the elution solvent tetrahydrofuran flow rate lml/min flows in the column (column temperature 4〇 °C) and dissolves Further, the following numerical average molecular weight (hereinafter referred to as Μη) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene 値. <Synthesis Example 1 &gt; By making HBPDA 18. Og' BP DA 4.54g' ΗΒΡΑ 15.9g' THPA 2.01g, BTEAC 0.19g In PGMEA 95.1g, the reaction was carried out at 120 °C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P1). The obtained polyester had a Μη of 1510 and a Mw of 3570. &lt;Synthesis Example 2 &gt; By reacting HBPDA 12.0 g, HBPA 10.2 g, THPA 0.95 g, BTEAC 0.22 g in PGMEA 54.8 g at 120 ° C 19 Hours, 俾 can get polyester solution (solid content concentration: 30.0 Quality %) ( P2). The obtained polyester had a Tn of 2820 and a Mw of 4,200. &lt;Synthesis Example 3 &gt; Polyester was obtained by reacting HBPDA 18.0 g, BPADA 7.37 g, HBPA 17.0 g, THPA 2.15 g, and BTEAC 0.10 g in PGMEA 104 g at 120 ° C for 19 hours. Solution (solid content concentration: 3 0.0% by mass) (P3). The obtained polyester had a Tn of 1640 and Mw of 3480 - 38 to 201105737 &lt; Synthesis Example 4 &gt; By making DA-4P 10.23 g (〇.〇35 mol), THPA 10.64 g (0.070 mol) in PGME 48.71 g The reaction was carried out at 23 ° C for 24 hours to obtain a solution of a carboxylic acid compound containing an amine group (solid content concentration: 3 〇·〇% by mass) (A 1 ). &lt;Synthesis Example 5 &gt; An amine group-containing carboxy group was obtained by reacting DA-1M 15.14 g (0.03 5 mol) and THPA l〇-64 g (0.070 mol) in PGME 60.15 g at 23 ° C for 24 hours. Acid compound solution (solids concentration: 3〇.0 mass%) (A 2 ). &lt;Synthesis Example 6 &gt; By reacting DA-4P 10.23 g (0.03 5 mol ) and iridium 13.45 g (0.070 mol) in PGME 55.25 g at 23 ° C for 24 hours, an amide group-containing carboxylic acid compound was obtained. Solution (solid content concentration: 3 Ο · 0 mass%) (A3). &lt;Synthesis Example 7 &gt; By reacting DDM 6.94 g (0.035 mol) and cesium 13.45 g (0.070 mol) in PGME 40.78 g at 23 ° C for 24 hours, a carboxylic acid compound solution containing an amine group was obtained. Solid content concentration: 30.0% by mass) (A4). -39-201105737 &lt;Synthesis Example 8 &gt; By reacting CBDA 17.7 g and pDA 10.2 g in NMP 66.4 g at 23 ° C for 24 hours, a polyimine precursor solution (solid concentration) was obtained. : 30.0 mass. /.) (P4). The obtained polybendimimine precursor had a Μη of 5,800 and a Mw of 1 2 5 00. &lt;Synthesis Example 9 &gt; MAA 1 〇.9 g, CHMI 3 5.3 g, HEMA 25.5 g, MMA 28.3 g were used as a monomer component, and AIBN 5 g was used as a radical polymerization initiator, and these were used in a solvent PGMEA 150 g. The polymerization was carried out at a temperature of from 60 ° C to 100 ° C to obtain an acrylic copolymer solution (solid content concentration: 40.0% by mass) (P5). The obtained acrylic copolymer solution had a Tn of 3 800 and a Mw of 6,700. &lt;Example 1 to Example 9 and Comparative Example 1 to Comparative Example 3 &gt; The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1, for each Evaluation of planarization, solvent resistance, transmittance, and alignment. -40- 201105737

(Α) Component* Solution (g) (B) Component (g) (C) Component (g) (D) Component (g) Solvent (g) Example 1 P1 20 CEL 1. 2 A1 2. 0 - PGME 8* 0 Example 2 P1 20 CEL 1. 2 A1 4. 0 — PGME 8. 4 Example 3 P1 20 CEL 1· 2 A1 8. 0 One PGME 9. 2 Example 4 P1 20 CEL 1. 2 A2 3 0 BMI1 0. 6 PGME 10. 0 Example 5 P1 20 CEL 1. 2 A2 3. 0 — PGME 8. 2 Example 6 P1 20 CEL 1. 2 A3 3. 0 — PGME 8. 2 Example 7 P1 20 CEL 1. 2 A4 3. 0 BMI1 0. 6 PGME 10. 0 Example 8 P2 20 CEL 1. 2 A2 3. 0 BMT1 0. 6 PGME 10. 0 Example 9 Comparative Example 1 P3 20 P1 20 CEL 1 2 A2 3. 0 BMI1 0. 6 PGME 10. 0 — - PGMEA 2. 22 Comparative Example 2 P4 20 CEL 1. 2 - NMP 2. 97 Comparative Example 3 P5 20 CEL 1. 2 A PGMEA 2. 80 ※P1 ~P 3 : Polyester solution, P4: Polyimine precursor solution, P5: Acrylic copolymer solution [Evaluation of planarization property] Each of Examples 1 to 9 and Comparative Examples 1 to 3 was subjected to The composition was coated on a stepped substrate (glass made of sorghum 5 μm, line width 10 μm, line pitch 50 μm) using a spin coater, and then heated at a temperature of 100 ° C on a hot plate. Prebaking was performed 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 is heated at a temperature of 23 ° C for 30 minutes, and then post-baked to form a film thickness of 2.5 μm. -41-201105737 Membrane. The film thickness of the coating film on the step substrate production line and the gap is measured. The flatness (〇1), the flattening ratio (DOP) =100x [l-{film thickness difference (μιη) / the height of the step substrate (0·5μιη) }], and the flattening rate 〇[ Evaluation of Solvent Resistance] Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was coated on a tantalum wafer using a spin coater, and then placed on a hot plate at a temperature of 100 ° C. Prebaking was carried out 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 23 ° C for 30 minutes by this coating film to form a cured 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. When PGMEA or yttrium was used, the film thickness was not changed, and the film thickness was reduced as X. [Evaluation of Light Transmittance (Transparency)] The respective compositions of Examples 1 to 9 and Comparative Example 3 were coated on a quartz substrate using a spin coater at a temperature of 1 ° C. Prebaking was performed on a hot plate for 12 sec to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The resulting film was post-baked on a hot plate at a temperature of 23 Torr for 30 minutes to form a cured film. • 42- 201105737 This cured film was measured for wavelength transmittance using an ultraviolet-visible spectrophotometer (manufactured by SHIMADSU UV-2550). [Evaluation of Orientation] The coatings of Examples 1 to 9 and Comparative Examples 1 to 1 were applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate for 120 seconds to form a film. The thickness of 2.8 μm was measured using F20 manufactured by FILMETRICS. The post-baking was carried out on a hot plate at 23 ° C for 30 minutes to form a rubbing treatment at a rotational speed of 300 rpm and a transport speed of 0.45 mm. Wash the scrubbed water for 5 minutes. On the substrate, the liquid crystal single phase difference material is coated with a spin coater, and then prebaked on a hot plate at 1 〇〇 ° C for 40 seconds to form a film thickness of 1.1 μm. Exposure at 20 〇〇 mJ in the environment. The alignment plate was prepared to visually confirm the alignment. If the substrate is tilted without tilting, the light transmittance is significantly changed as a defect, and [heat resistance evaluation]

The coatings of Examples 1 to 9 and Comparative Examples 1 to 1 were applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate for 12 seconds, at a temperature of 230 ° C ( Share) Shimadzu's composition of 3 at 400 nm is 1 〇 0 °C in addition to the coating film. Film This film is a hard cured film. 10 m m / s, the substrate is composed of pure body seconds, 55 ° C 3 0 coating film. When the substrate is held at 45 degrees, the changer is subjected to post-baking for 30 minutes on a hot plate at -43 to 201105737 to form a cured film. The film thickness is F20 manufactured by FILMETRICS. And measured. Thereafter, the cured film was further fired on a hot plate at a temperature of 230 ° C for 60 minutes, and the film thickness was measured again to calculate the rate of change in film thickness from post-baking. Further, it can be seen that the cured film having heat resistance is desired to have at least a film thickness change rate of ± 5% or less. [Results of Evaluation] The results of the above evaluations are shown in Table 2 below. [Table 2] Flattening Rate Solvent Resistance Alignment Heat Resistance Transmittance (%) PGMEA NMP (%) (%) Example 1 82 〇〇〇1 2 93 Example 2 80 〇〇〇-2 91 Example 3 76 〇〇〇-3 90 Example 4 85 〇〇〇-2 1 96 Example 5 83 〇〇〇-1 96 Example 6 80 〇〇〇1 2 90 Example 7 81 〇〇〇-2 92 Example 8 80 〇〇〇-1 98 Example 9 88 〇〇〇-1 94 Comparative Example 1 XX - - Comparative Example 2 25 〇〇〇 1 3 85 Comparative Example 3 88 〇〇X -0· 5 96 Example 1 to 9 are flattening ratio and high heat resistance. For any of PGMEA 'NMP, resistance can be seen. In addition, all of them showed good alignment, and high transmittance was achieved even after high-temperature firing (transparency - 44 - 201105737. Further, Comparative Example 1 did not form a cured film. Further, Comparative Example 2 was solvent resistant and heat resistant. Although the properties and the alignment were good, the flattening rate was extremely low. Then, in Comparative Example 3, the flatness, heat resistance, solvent resistance, and transmittance were excellent, but the results were poor in the alignment. In the case of forming a cured film of a polyester composition for forming a thermosetting film of the present invention, a glycol solvent such as propylene glycol monoether ether acetate can be used, and the obtained cured film is excellent in light transmittance and solvent resistance. Good results can be obtained by the performance of any of properties, heat resistance, flatness, and alignment. [Industrial Applicability] The polyester composition for forming a thermosetting film of the present invention is very useful for optical use. The liquid crystal alignment layer of the anisotropic film or the liquid crystal display element is further suitable as a protective film in various displays for forming a thin film transistor (TFT) type liquid crystal display element, an organic EL element, or the like. A material of a cured film such as a flattening film or an insulating film, in particular, an interlayer insulating film of a TFT-type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, etc. [Prior Art] [Patent Literature] [Patent Document 1] JP-A-2000-119472 (Patent Document 3) JP-A-2005-79077 Fig. 1 is a schematic view showing a cured film formed when a polyester composition for forming a thermosetting film of the present invention is applied to a step substrate. Fig. 2 is a liquid crystal cell (a) in which a liquid crystal alignment film is formed by a conventional technique. A pattern diagram in which a liquid crystal cell (b) which forms a planarizing film is formed by using a thermosetting film of the present invention to form a flattening film. -46-

Claims (1)

201105737 VII. Application for patents: 1. A polyester composition for forming a thermosetting film, which comprises (A) component, (B) component and (C) component; (A) component: tetracarboxylic acid Polyester obtained by reacting an anhydride with a diol compound, (B) component: an epoxy compound having two or more epoxy groups, and (C) component: an amine group-containing group obtained by reacting a diamine compound with a dicarboxylic anhydride Carboxylic acid compound. 2. The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (A) contains a polyester having a structural unit represented by the following formula (1); (wherein, A represents a tetravalent organic group to which four bonding bonds have been bonded on an alicyclic group or an aliphatic group, and B represents two bonding bonds on an alicyclic group or an aliphatic group. A 2 valent organic group). 3. The polyester composition for forming a thermosetting film according to the second or second aspect of the patent application, wherein the component (A) is a tetrahydro acid dianhydride represented by the following formula (i) and a formula (ii) The polyester obtained by the reaction of the diol compound shown-47-201105737 〇(i) ΗΟ-Β-ΟΗ (Μ) (wherein Α represents a tetravalent organic group to which four bonding bonds are bonded to an alicyclic group or an aliphatic group, and B represents an alicyclic group. Or a divalent organic group to which two bonding bonds have been bonded on the aliphatic group. 4. The polyester composition for forming a thermosetting film according to the second or third aspect of the invention, wherein in the above formula (1), A is represented by the following formula (A-1) to formula (A-8). The at least one selected from the group 'B' is not at least one selected from the group represented by the following formula (B-1) to (B-5). (B-1) (B-2) (B-3) (B-4) The polyester composition for forming a thermosetting film according to any one of claims 1 to 4, wherein (A) The weight average molecular weight of the polyester of the component is from 1,000 to 30,000 in terms of polystyrene. -48-201105737 6. The polyacetate composition for forming a thermosetting film according to any one of claims 1 to 5, wherein the component (C) is a 1,3-mol and a monocarboxylic acid anhydride. The amine group-containing carboxylic acid compound obtained by the reaction of 7 to 2 moles. The polyester composition for forming a thermosetting film according to any one of the first to sixth aspects of the invention, wherein the component (B) is contained in an amount of 3 to 50 parts by mass based on 100 parts by mass of the component (A). ~50 parts by mass of component (C). 8. The polyester composition for forming a thermosetting film according to any one of the above claims, further comprising a bismaleimide compound as the component (D). 9. The polyester composition for forming a thermosetting film according to the eighth aspect of the invention, wherein the component (D) is contained in an amount of from 5 to 50 parts by mass based on 1 part 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 9. A liquid crystal alignment layer is obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 9. -49 -