Polymer composition, liquid crystal alignment agent, resin film, liquid crystal alignment film, manufacturing method of liquid crystal display element, and liquid crystal display element

Abstract

This invention provides a polymer composition suitable for obtaining a liquid crystal alignment film with excellent resistance to AC image retention and a low pretilt angle. A polymer composition is characterized by containing the following (A) and (B) components: (A) Component: Polymer (A), selected from at least one polyimide precursor having a repeating unit represented by formula (a) and polyimides that are amides of the polyimide precursor. (B) Component: Polyester (B), having a repeating unit represented by formula (b1) and not containing the repeating unit represented by formula (a) and its amide structure. The definitions of each designation are as described in the specification.

Description

Technical Field

[0001] This invention relates to a method for manufacturing polymer compositions, liquid crystal alignment agents, resin films, liquid crystal alignment films, liquid crystal display elements, and liquid crystal display elements. Prior Technology

[0002] Liquid crystal display (LCD) elements used in LCD TVs, navigation devices, smartphones, etc., typically contain a liquid crystal alignment film to control the alignment of the liquid crystals. The liquid crystal alignment film controls the alignment of the liquid crystal molecules within the LCD element to a specific direction. For example, an LCD element may have a structure where liquid crystal molecules, forming the liquid crystal layer, are held between liquid crystal alignment films formed on the surfaces of a pair of substrates. The liquid crystal molecules align in a specific direction due to the liquid crystal alignment film and respond to the voltage applied to electrodes located between the substrate and the liquid crystal alignment film. As a result, the LCD element displays the desired image by utilizing the alignment change caused by the response of the liquid crystal molecules. Currently, the main type of liquid crystal alignment film used is a polyimide-based liquid crystal alignment film, formed by coating a liquid crystal alignment agent, primarily composed of polyimide precursors such as polyamic acid and a solution of soluble polyimide, onto a glass substrate and then calcining it. In recent years, with the increasing performance of liquid crystal display elements, in addition to applications such as large-screen and high-definition LCD TVs, liquid crystal display elements are also used in automotive applications, such as car navigation systems, dashboards, surveillance cameras, and medical camera screens. Considering the requirements of viewing angle characteristics, some people have explored transverse electric field methods such as IPS (In-Plane Switching) and FFS (Fringe Field Switching) (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] International Publication No. 2019-082975 Summary of the Invention

[0004] (The problem the invention aims to solve)

[0005] The liquid crystal alignment film used in IPS and FFS driving liquid crystal display elements needs to have alignment regulation force to suppress image retention (hereinafter also referred to as AC image retention) caused by long-term AC driving. In the rapidly improving precision of liquid crystal display elements, high display quality is considered important, and the specifications for display defects known as "image retention" are becoming increasingly stringent. Furthermore, with the application of liquid crystal display elements in automotive applications, such as car navigation systems, dashboards, surveillance cameras, and medical camera screens, a lower pre-tilt angle is required than before to further improve viewing angle characteristics.

[0006] In view of the above circumstances, the present invention aims to provide a polymer composition of a liquid crystal alignment agent suitable for obtaining a liquid crystal alignment film with excellent resistance to AC image retention and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film. (Methods for solving problems)

[0007] In order to achieve the above-mentioned objectives, the inventors of this invention conducted extensive research and discovered that forming a resin film using a polymer composition containing specific components was effective in achieving the above objectives, thus completing this invention.

[0008] This invention is based on this insight and is based on the following points. A polymer composition characterized by containing the following components (A) and (B), (A) Component: Polymer (A), selected from at least one polyimide precursor having repeating units represented by formula (a) and polyimides constituting amides of the polyimide precursor. (B) Composition: Polyester (B), having repeating units represented by formula (b1) but not having repeating units represented by formula (a) and their amide structure. [Chemistry 1] X represents a tetravalent organogroup, Y represents a divalent organogroup derived from a diamine, the two Rs each independently represent a hydrogen atom or a monovalent organogroup, and the two Zs each independently represent a hydrogen atom or a monovalent organogroup. [Chemistry 2] Xar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or its derivatives, where each of the two R's independently represents a hydrogen atom or a monovalent organic group, and E represents a divalent organic group derived from an organic diol by removing the hydrogen atoms contained in the two hydroxyl groups. This organic diol contains a divalent organic group represented by the following formula (EG). [Chemistry 3] n is an integer greater than or equal to 5, and R represents a hydrogen atom or a methyl group. (Effects of the invention)

[0009] According to the present invention, a polymer composition of a liquid crystal alignment agent suitable for obtaining a liquid crystal alignment film with excellent resistance to AC image retention and a low pretilt angle, the liquid crystal alignment agent, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film can be obtained. Furthermore, the liquid crystal display element has a high display quality with few display defects. The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but it is generally presumed to be as follows: that is, by introducing a specific alkyl glycol chain into a specific polyester, the elongation of the film and the flatness of the film surface are improved, and thus it is believed that the above-mentioned effects can be obtained. Implementation

[0010] The following describes the components contained in the polymer composition disclosed herein, as well as other components that may be added as needed. In this specification, halogen atoms may include fluorine, chlorine, bromine, and iodine atoms. Boc represents the third butoxycarbonyl group.

[0011] <Polymer (A)> The polymer composition of the present invention comprises at least one polymer (A) selected from the group consisting of a polyimide precursor (hereinafter also referred to as polyimide precursor (A)) having a repeating unit represented by formula (a) above and a polyimide that is a polyimide derivative of the polyimide precursor. The polymer (A) may be one or more.

[0012] (Equation (a) represents the repeating unit) In formula (a) above, Y represents a divalent organic group derived from a diamine. Furthermore, a divalent organic group derived from a diamine is, for example, a divalent organic group from which two amino groups have been removed. Examples of diamines include the following. This diamine can be used alone or in combination of two or more.

[0013] Diamines represented by formula (O); diamines with photoalignment groups such as 4,4'-diaminoazobenzene or diaminodiphenylacetylene; diamines with amide or urea bonds such as diamines represented by formulas (h-1) to (h-6); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene; diamines represented by formula (do); 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine Pyridine, 3,6-diaminophenazole, N-methyl-3,6-diaminophenazole, 1,4-bis-(4-aminophenyl)-guanidine, 3,6-diaminoacridine, N-ethyl-3,6-diaminophenazole, N-phenyl-3,6-diaminophenazole, N-[3-(1H-imidazol-1-yl)propyl]3,5-diaminobenzylamine, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-azolyl]-aniline, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-azolyl]-aniline, 1,4-bis(p-aminobenzyl)guanidine, 4,4'-propane-[1,3-dimethylbis(guanidine-1-yl)-[4-diaminobenzyl] ... [4-diyl]diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)guanidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[aniline], 1,4-bis-(4-aminophenyl)-guanidine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazol-2-yl)phenyl-1,3-diamine, or formulas (z-1) to (z-5). The term "diamine" refers to a diamine containing a heterocyclic ring, such as 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-phenylenediamine, which has a diphenylamine structure. It is a structure having at least one nitrogen-containing group selected from the group consisting of a nitrogen-containing heterocycle, a secondary, or a tertiary amine group (excluding amine groups from -N(D)- (where D represents a protecting group that will be removed and replaced by a hydrogen atom upon heating). These are also referred to below as specific nitrogen-containing structures.) of diamines; 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl Diamines containing carboxyl groups, such as 4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-dihydroindene-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; 2-(2,4-diaminophenyl)methacrylate. Diamines with photopolymerizable groups at the end, such as aminophenoxyethyl ester and 2,4-diamino-N,N-diallylaniline; diamines with steroidal skeletons, such as cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosterol 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by formulas (V-1) to (V-2); and diamines with the group "-N(D)-" (D represents a protecting group that will be removed and replaced by a hydrogen atom upon heating). The preferred diamine is a diamine with a tert-butoxycarbonyl group, preferably a diamine represented by formulas (d-1) to (d-7); a diamine having a siloxane bond, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane or a diamine represented by formula (Ds-1); or a diamine with two amino groups bonded to a styrene group, such as m-xylene diamine, 1,3-propane diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), or any of the formulas (Y-1) to (Y-167) disclosed in International Publication No. 2018 / 117239.

[0014] [Chemistry 4] Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring. The two Ars can be the same or different, and any hydrogen atom in the aforementioned benzene ring, biphenyl structure, or naphthalene ring can be substituted with a monovalent group. p is an integer of 0 or 1. Q2 represents -(CH2)n- (n is an integer from 2 to 18), or a group in which at least a portion of the -CH2- group of -(CH2)n- is substituted by any one of -O-, -C(=O)-, or -OC(=O)-.

[0015] [Chemistry 5]

[0016] [Chemistry 6] In equation (z-2), the two m can be the same or different.

[0017] [Chemistry 7] When there are two or more m atoms, the two or more m atoms can be the same or different. One or more hydrogen atoms on the benzene ring can also be substituted by a monovalent group.

[0018] [Chemistry 8] In formula (V-1), m and n each independently represent integers from 0 to 3 (only satisfying 1 ≤ m + n ≤ 4), j is an integer of 0 or 1, X1 represents -(CH2)a- (a is an integer from 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. R1 represents a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms. When two of m, n, X1, and R1 are present, each independently has the above definitions. In formula (V-2), X2 represents -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. [Chemistry 9] In equations (d-2), (d-6), and (d-7), R represents a hydrogen atom or -(CH₂)k-Boc (k is an integer from 0 to 3). Also, when k is 0, (CH₂)k represents a single bond. [Chemistry 10]

[0019] In the above formula (do), the monovalent group can include halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, fluoroalkyl groups with 1 to 10 carbon atoms, fluoroalkenyl groups with 2 to 10 carbon atoms, fluoroalkoxy groups with 1 to 10 carbon atoms, carboxyl groups, hydroxyl groups, alkoxycarbonyl groups with 1 to 10 carbon atoms, cyano groups, nitro groups, etc. Regarding the diamine represented by the above formula (do), considering the viewpoint of improving the alignment of liquid crystals, the diamines represented by the following formulas (do-1) to (do-6), 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ether are preferred. [Chemistry 11]

[0020] In the diamine represented by formula (O), any hydrogen atom of the benzene ring, biphenyl structure, or naphthalene ring can be substituted with a monovalent group. Examples of such monovalent groups include: halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, fluoroalkyl groups with 1 to 10 carbon atoms, fluoroalkenyl groups with 2 to 10 carbon atoms, fluoroalkoxy groups with 1 to 10 carbon atoms, alkoxycarbonyl groups with 1 to 10 carbon atoms, cyano groups, nitro groups, etc.

[0021] Regarding the diamine represented by formula (O) above, considering the viewpoint of improving liquid crystal alignment, the following formulas (O-1)~(O-8) can be listed: p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-dimethoxybenzyl, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(6-amino-2-naphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4 The diamines represented by 4'-diaminobiphenyl, 3-fluoro-4,4'-diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, or 2,7-diaminonaphthalene are preferred.

[0022] [Chemistry 12] In equation (o-8), the two m's can be the same or different.

[0023] The aforementioned Y is preferably a divalent organic group of a diamine selected from the group consisting of diamines represented by formula (O), diamines having amide or urea bonds, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamines represented by formula (do), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and diamines having the group "-N(D)-" (D represents a protecting group that will be removed and replaced by a hydrogen atom upon heating, preferably a tert-butoxycarbonyl group). By conforming to this configuration, the aforementioned Y can achieve the effect of reducing residual images generated by long-term AC driving, which is ideal.

[0024] In formula (a) above, X represents a tetravalent organic group. X preferably represents a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof. Furthermore, a tetravalent organic group derived from a tetracarboxylic dianhydride or a derivative thereof is, for example, a tetravalent organic group from which four carboxyl groups have been removed from the corresponding tetracarboxylic acid. Examples of such tetravalent organic groups include those derived from acyclic aliphatic tetracarboxylic dianhydrides or their derivatives, alicyclic tetracarboxylic dianhydrides or their derivatives, or aromatic tetracarboxylic dianhydrides or their derivatives. Here, the acyclic aliphatic tetracarboxylic dianhydride is obtained by intramolecular dehydration of the four carboxyl groups bonded to the chain hydrocarbon structure. However, it is not necessary for it to be composed solely of a chain hydrocarbon structure; a portion of it may also have an alicyclic or aromatic ring structure. Alicyclic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecularly dehydrating four carboxyl groups, including at least one carboxyl group bonded to an alicyclic structure. However, none of these four carboxyl groups are bonded to an aromatic ring. Furthermore, they do not necessarily consist solely of an alicyclic structure; a portion of them may also possess a chain hydrocarbon structure or an aromatic ring structure. Aromatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group linked by an aromatic ring. However, they do not necessarily have to consist solely of an aromatic ring structure; some of them may also have a chain hydrocarbon structure or an alicyclic structure. The derivatives of the aforementioned tetracarboxylic dianhydrides can be listed as tetracarboxylic dihalides, tetracarboxylic dialkyl esters, or tetracarboxylic dialkyl ester dihalides. The tetracarboxylic dianhydride or its derivatives can be used alone or in combination of two or more.

[0025] Among the aforementioned acyclic aliphatic or alicyclic tetracarboxylic dianhydrides, or their derivatives, considering the viewpoint of improving liquid crystal alignment, tetracarboxylic dianhydrides or their derivatives having at least one substructure selected from the group consisting of cyclobutane ring structures, cyclopentane ring structures, and cyclohexane ring structures are preferred.

[0026] The aforementioned X is preferably a tetravalent organic group derived from a tetracarboxylic dianhydride or its derivative represented by the following formula (t).

[0027] [Chemistry 13] In the formula, X1 is a structure selected from formulas (X1-1) to (X1-25). * indicates an atomic bond. Also, X1 is a tetracarboxylic dianhydride represented by formula (t) of formulas (X1-1) to (X1-23), an example of an acyclic aliphatic or alicyclic tetracarboxylic dianhydride. Also, X1 is a tetracarboxylic dianhydride represented by formula (t) of formulas (X1-24) to (X1-25), an example of an aromatic tetracarboxylic dianhydride.

[0028] [Chemistry 14]

[0029] [Chemistry 15]

[0030] [Chemistry 16]

[0031] [Chemistry 17]

[0032] In formulas (X1-1) to (X1-4), R1 to R21 independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organogroup with 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * indicates an atomic bond. Considering the viewpoint of improving the alignment of liquid crystals, it is more ideal for R1 to R21 to be a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, with hydrogen atom or methyl group being more ideal. In equations (X1-24) to (X1-25), j and k are integers of 0 or 1, and A1 and A2 independently represent single bonds, -O-, -CO-, -COO-, phenyl, sulfonyl, or amino groups. Multiple A2s can be the same or different.

[0033] Specific examples of equation (X1-1) can be listed in equations (1-1) to (1-6). Considering the viewpoint of improving the alignment of liquid crystals, equations (1-1) and (1-2) are particularly good. *Synonyms with the above.

[0034] [Chemistry 18]

[0035] Ideal concrete examples of the above equations (X1-24) and (X1-25) can be listed as equations (X1-26) to (X1-41). *Synonymous with the above. [Chemistry 19] [Chemistry 20]

[0036] From the perspective of improving the alignment of liquid crystals, the above X 1 is more ideal as (X1-1)~(X1-10), (X1-18)~(X1-23), (X1-24)~(X1-25), or (X1-26)~(X1-30), the above X 1 is better as (X1-1), (X1-5), (X1-7)~(X1-10), (X1-21), (X1-23), (X1-24)~(X1-25), or (X1-26)~(X1-30), and the above X 1 is more ideal as (1-1), (1-2), (X1-5), (X1-7), (X1-9), or (X1-26)~(X1-30).

[0037] In formula (a) above, the monovalent organic groups of R and Z can be listed as monovalent hydrocarbon groups with 1 to 20 carbon atoms. The methylene group of this hydrocarbon group is represented by -O-, -S-, -CO-, -COO-, -COS-, -NR 3- (where R 3 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms), -CO-NR 3- (where R 3 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms), -Si(R 3) 2- (where R 3 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms), -SO A monovalent group A formed by 2-or equivalent substitution is formed by substituting at least one hydrogen atom of a monovalent hydrocarbon group or a carbon atom bonded to a monovalent group A with a halogen atom, hydroxyl group, alkoxy group, nitro group, amino group, mercapto group, nitroso group, alkylsilyl group, alkoxysilyl group, silyl alcohol group, sulfinic acid group, phospho group, carboxyl group, cyano group, sulfonyl group, acetyl group, etc., and is a monovalent group with a heterocyclic ring. Among the monovalent organic groups R and Z in formula (a) above, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkynyl groups with 2 to 10 carbon atoms, tributoxycarbonyl groups, or 9-pyromethoxycarbonyl groups are preferred, alkyl groups with 1 to 3 carbon atoms are more preferred, and methyl groups are even more preferred. From the perspective of achieving the effects of this invention, it is more ideal for R and Z to be hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and even more ideal for hydrogen atoms or methyl groups.

[0038] In equation (a) above, X, Y, R, and Z can each be one type or two or more types. The ideal proportion of polymer (A) in 100 parts by mass of polymer composition is 70-99 parts by mass, and even more ideal is 80-98 parts by mass.

[0039] (Repeating units constituting polymer (A)) The polymer (A) in this invention is selected from at least one polymer composed of a polyimide precursor having a repeating unit represented by formula (a) above and a polyimide that is a polyimide derivative of the polyimide precursor. The polymer (A) may also have a repeating unit represented by formula (a) above and a terminal group.

[0040] Here, a terminal group refers to a group that is bonded at the end of the repeating unit constituting the polymer (A) described above. Examples of terminal groups include amine, carboxyl, anhydride, isocyanate, or derivatives thereof. Amine, carboxyl, anhydride, and isocyanate groups can be obtained by conventional condensation reactions, and the derivatives thereof, as described later, can be obtained, for example, by sealing the terminal groups using a capping agent.

[0041] The sum of the repeating units represented by formula (a) and their amide structures should ideally be 10 mol% or more of the total repeating units constituting polymer (A), and even more ideally 20 mol% or more.

[0042] (Equation (U) represents the repeating unit) The polymer (A) in this invention may also have repeating units represented by the following formula (U). [Chemistry 21] U1 is a divalent organic group, U1' is a divalent organic group derived from diamine, and C1 and C1' are each independently a hydrogen atom or a monovalent organic group.

[0043] In the above formula (U), U1 is a divalent organic group. Examples of U1 can be derived from divalent organic groups of diisocyanates. The diisocyanate can be used alone or in combination of two or more. Here, diisocyanates, such as aromatic diisocyanates and aliphatic diisocyanates. Here, "aromatic diisocyanate" refers to a diisocyanate having at least one aromatic group. "Aliphatic diisocyanate" refers to a diisocyanate having an aliphatic group but no aromatic group. U 1, for example: (i) from a diisocyanate structure (O=C=NRN=C=O) where R is a divalent organic group of an aromatic diisocyanate having at least one benzene ring with 6 to 30 carbon atoms, or (ii) from a diisocyanate structure (O=C=NRN=C=O) where R is a divalent organic group of an aliphatic diisocyanate having an aliphatic group and no aromatic group with 4 to 30 carbon atoms. Furthermore, aliphatic groups include either non-cyclic aliphatic groups or alicyclic groups. Specific examples of U 1 may include those derived from o-phenyl diisocyanate, m-phenyl diisocyanate, p-phenyl diisocyanate, toluene diisocyanates (e.g., 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,4-2-methoxybenzene diisocyanate, xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, 4,4'-diisocyanate diphenyl ether, 2,2'-bis(4-diisocyanate phenyl)propane, 4,4'- Diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), diphenyl ether diisocyanate, diphenyl 4,4'-diphenyl ion diisocyanate, diphenyl ion diisocyanate, diphenyl ion diisocyanate, and diphenyl ion diisocyanate (2,2'-diphenyl ketone diisocyanate) are divalent organic groups derived from aromatic diisocyanates, as well as divalent organic groups derived from aliphatic diisocyanates such as isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and tetramethylene diisocyanate.

[0044] In the above formula (U), U1' is a divalent organic group derived from a diamine. Diamines can be exemplified by the repeating unit (a) above, with the ideal form as described above.

[0045] In formula (U) above, the monovalent organic groups of C1 and C1' can be represented by the structures exemplified by R and Z in the repeating unit (a) above. From the viewpoint of obtaining the effect of the present invention, it is more ideal for C1 and C1' to be hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and even more ideal for hydrogen atoms or methyl groups.

[0046] In the above formula (U), U1, U1', C1, and C1' can each be one type or two or more types.

[0047] In the present invention, when the polymer (A) has the repeating unit represented by the above formula (U), from the viewpoint of obtaining the effect of the present invention, the content ratio of the repeating unit represented by formula (U) relative to the above repeating unit (a), the amide structure of repeating unit (a) and the repeating unit represented by formula (U) totaling 100 mol% is more ideally 1~30 mol%, and more ideally 2~25 mol%.

[0048] <Polyester (B)> The polymer composition of the present invention contains a polyester (B) having repeating units represented by formula (b1) above but not having repeating units represented by formula (a) above and their amide structure. Polyester (B) can be used alone or in combination of two or more.

[0049] In formula (b1) above, X ar represents a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride or its derivative. Furthermore, aromatic tetracarboxylic acid dianhydrides are acidic dianhydrides obtained by intramolecularly dehydrating four carboxyl groups, including at least one carboxyl group linked by an aromatic ring. However, they do not necessarily have to be composed solely of an aromatic ring structure; a portion of them may also have a chain hydrocarbon structure or an alicyclic structure. In formula (b1) above, X ar is preferably a tetravalent organic group derived from tetracarboxylic dianhydride or its derivative represented by formula (t) below. [Chemistry 22] In the formula, X1 is selected from the structures in the following formulas (X1-24) and (X1-25). * indicates an atomic bond. [Chemistry 23] In equations (X1-24) to (X1-25), j and k are integers of 0 or 1, and A1 and A2 independently represent single bonds, -O-, -CO-, -COO-, phenyl, sulfonyl, or amino groups. Multiple A2s can be the same or different.

[0050] Ideal concrete examples of the above equations (X1-24) and (X1-25) can be listed as equations (X1-26) to (X1-41). *Synonyms with the above. [Chemistry 24] [Chemistry 25]

[0051] In formula (b1) above, E represents a divalent organic group formed by removing the hydrogen atoms from the two hydroxyl groups of the organic diol. The aforementioned organic diol contains the divalent organic group represented by formula (EG). Organic diols containing the divalent organic group represented by formula (EG) are not particularly limited as long as the molecule contains formula (EG), but it is preferable for diols with hydrogen atoms bonded to both ends of formula (EG). For diols with hydrogen atoms bonded to both ends of formula (EG), the upper limit of n is preferably set to be below 5,000 (preferably below 4,000), and below 3,000. Considering the improvement of liquid crystal alignment, an upper limit of n of 40 is preferable, 30 is better, and 20 is especially preferable. For the lower limit of n, considering the improvement of liquid crystal alignment, 5 is preferable, and 6 is even better.More specifically, diols containing the divalent organic group represented by the above formula (EG) can be listed as pentaethylene glycol, hexaethylene glycol, and, according to Sanyo Chemical Industries Co., Ltd., the trade names PEG-300, PEG-400, PEG-600, PEG-1000, PEG-1500, PEG-2000, PEG-4000N, PEG-4000S, PEG-6000E, PEG-6000P, PEG-10000, PEG-13000, and PEG-20000; and, according to Merck, the product names PEG300, PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, PEG20000, and PEG3. 5000; SIGMA-ALDRICH manufactured products with serial numbers P2139, P3265, P3515, 81210, 81240, 81260, 81285, 81310, 181986, 181994, 182001, 182028, 189456, 202304, 202312, 202320, 2 02339, 202398, 202421, 202436, 202444, 202452, 295906, 309028, 372773, 372781, 373001, 412325, 435406, 435422, 435457, 637726; Trade name SINOPOL manufactured by Chung-Ji Synthetic Chemicals Co., Ltd. PEG600, SINOPOL PEG1500, SINOPOL PEG4000; LION SPECIALTY CHEMICALS products under the trade names PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#4000, PEG#6000M; and Tokyo Kasei Kogyo Co., Ltd. products under the trade names Polyethylene Glycol 400 and Polyethylene Glycol 600 are sold in the market.Ideal concrete examples of diols with hydrogen atoms bonded at both ends of the above formula (EG) include pentaethylene glycol, hexaethylene glycol, PEG-300, PEG-400, PEG-600, and PEG-1000 manufactured by Sanyo Chemical Industries, PEG300 and PEG1000 manufactured by Merck, SINOPOL PEG600 and SINOPOL PEG1000 manufactured by Chunghwa Synthetic Chemicals, PEG#300, PEG#400, PEG#600, and PEG#1000 manufactured by Lion Specialty Chemicals, and Polyethylene Glycol 400 and Polyethylene Glycol manufactured by Tokyo Chemical Industries. 600 represents polyethylene glycol, or pentapropylene glycol, hexapropylene glycol, polypropylene glycol (preferably with an average molecular weight of 400-5,000), and copolymers of ethylene oxide and propylene oxide with an average molecular weight of 500-5,000. The aforementioned polyethylene glycol and polypropylene glycol can also be obtained by anionic ring-opening polymerization of ethylene oxide and propylene oxide. This polymerization reaction can be carried out using water, ethylene glycol, propylene glycol, and a catalyst amount of alkali (e.g., potassium hydroxide). Furthermore, the average molecular weight of diols containing the divalent organic groups represented by (EG) is the weight average molecular weight obtained using gel permeation chromatography (GPC) with polystyrene as the reference.

[0052] The proportion of repeating units represented by formula (b1) above is preferably 10 mol% or more of all repeating units constituting polyester (B), and even more preferably 20 mol% or more. When other repeating units are included, the upper limit is preferably 90 mol% or less, and even more preferably 80 mol% or less.

[0053] (Equation (b2) represents the repeating unit) Polyester (B) may also have repeating units represented by the following formula (b2). Polyester (B) may also not have repeating units represented by the following formula (b2). [Chemistry 26] A1 is derived from the divalent organic group of diisocyanate. A2 is derived from the divalent organic group of organic diol by removing the hydrogen atoms contained in the two hydroxyl groups.

[0054] In formula (b2) above, A1 is derived from the divalent organic group of the diisocyanate. Furthermore, it can be derived from the divalent organic group of the diisocyanate, for example, from a diisocyanate in which two isocyanate groups (-N=C=O) have been removed. This diisocyanate can be used alone or in combination of two or more. Here, diisocyanates include, for example, diisocyanates (DI EG) having a divalent organic group represented by the above formula (EG), aromatic diisocyanates and aliphatic diisocyanates other than diisocyanates (DI EG). Here, "aromatic diisocyanate" refers to a diisocyanate having at least one aromatic group. "Aliphatic diisocyanate" refers to a diisocyanate having an aliphatic group but no aromatic group. The above-mentioned diisocyanates (DI EG) are, for example, diisocyanates represented below. [Chemistry 27]

[0055] Aromatic and aliphatic diisocyanates other than diisocyanates (DI EG), for example: (i) in a diisocyanate structure (O=C=NRN=C=O), R is an aromatic diisocyanate that does not have a divalent organic group represented by the above formula (EG) and has at least one benzene ring with a carbon number of 6 to 30; or (ii) in a diisocyanate structure (O=C=NRN=C=O), R is an aliphatic diisocyanate that has an aliphatic group and does not have a divalent organic group represented by the above formula (EG) or an aromatic organic group with a carbon number of 4 to 30. Furthermore, aliphatic groups include non-cyclic aliphatic groups and alicyclic groups. Specific examples of aromatic and aliphatic diisocyanates other than diisocyanates (DI EG) include o-phenyl diisocyanate, m-phenyl diisocyanate, p-phenyl diisocyanate, toluene diisocyanates (e.g., 2,4-toluene diisocyanate, 2,6-toluene diisocyanate), 1,4-methoxybenzene diisocyanate, xylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate biphenyl, and 4,4'-diisocyanate diphenyl ether. Aromatic diisocyanates such as 2,2'-bis(4-phenyl diisocyanate)propane, 4,4'-diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate), 4,4'-diphenyl guanidine diisocyanate, 3,3'-diphenyl guanidine diisocyanate and 2,2'-diphenyl ketone diisocyanate, as well as aliphatic diisocyanates such as isophorone diisocyanate, norcamphene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate and tetramethylene diisocyanate.

[0056] In formula (b2) above, A2 is a divalent organic group from which two hydrogen atoms from the two hydroxyl groups have been removed. This organic diol can be used alone or in combination of two or more. Examples of this organic diol include diols containing the divalent organic group represented by formula (EG) above; and diols not containing the divalent organic group represented by formula (EG) above. Specific examples of diols that do not contain the divalent organic group represented by the above formula (EG) include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanediol, isoalkyl diols; dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutyric acid (2,2-bis(hydroxymethyl)propionic acid), etc. Carboxyl-containing diols such as methyl butyric acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,5-dihydroxybenzoic acid; polypropylene glycol; random copolymers of polypropylene glycol and neopentyl glycol; polyester diols obtained by reacting polyols with polybasic acids; polycarbonate diols with a carbonate backbone; polycaprolactone diols obtained by ring-opening addition reactions of lactones such as γ-butyl lactone, ε-caprolactone, and δ-valerolactone; bisphenol A; propylene oxide adducts of bisphenol A; hydrogenated bisphenol A; propylene oxide adducts of hydrogenated bisphenol A, etc. Specific examples of diols containing a divalent organic group represented by the above formula (EG) include ideal examples of diols exemplified in the repeating unit (b1) above.

[0057] (The repeating unit that constitutes polyester (B)) The polyester (B) of this invention is a polyester having the repeating unit represented by formula (b1) above but not having the repeating unit represented by formula (a) above and its amide structure. The polyester (B) of this invention may also have the above-described repeating unit and terminal groups. Regarding the terminal groups, it is as described above.

[0058] When polyester (B) contains repeating units represented by formula (b2) above, the proportion of repeating units represented by formula (b2) above should ideally be 10 mol% or more of the total repeating units constituting polyester (B), and more than 20 mol% is even more ideal. Furthermore, 90 mol% or less is even better, and 80 mol% or less is even better. Furthermore, when A2 is a divalent organic group of a diol with hydrogen atoms bonded to both ends of the above formula (EG), the proportion of the repeating unit represented by formula (b2) should ideally be 10 mol% or more of the total repeating units constituting polyester (B), more than 20 mol% is preferred, and more than 50 mol% is even more preferred. Moreover, it is preferable to have an upper limit of 90 mol% or less, and even more preferable to have an upper limit of 80 mol% or less.

[0059] In the above formula (b2), A1 and A2 can each be one type or two or more types. In this invention, the proportion of polyester (B) should ideally be 1 to 30 parts by mass per 100 parts by mass of the polymer composition, and more ideally 2 to 20 parts by mass.

[0060] <Manufacturing of Polymer (A)> The polyimide precursor of the polymer (A) mentioned above is, for example, polyamide, polyamide ester, etc. Polyamide (a polyimide precursor having a repeating unit represented by formula (a) where R is a hydrogen atom) can be manufactured by the following method. Specifically, a tetracarboxylic acid component containing the above-mentioned tetracarboxylic dianhydride or its derivative and a diamine component containing the above-mentioned diamine can be reacted in the presence of an organic solvent, preferably at -20 to 150°C, more preferably at 0 to 50°C, preferably for 30 minutes to 24 hours, and more preferably for 1 to 12 hours (condensation polymerization) to synthesize the above-mentioned polyamide containing the above-mentioned repeating unit (U). When the above-mentioned polyamide contains the above-mentioned repeating unit (U), it can be synthesized by reacting a diisocyanate compound represented by O=C=NU 1-N=C=O (U 1 is the same as U 1 in formula (U)) with the above-mentioned tetracarboxylic acid component and the above-mentioned diamine component. Specific examples of organic solvents used in the above reactions include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidineone. Furthermore, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by formulas [D-1] to [D-3] can be used. Two or more of these solvents can also be mixed.

[0061] [Chemistry 28] In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms; in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms; and in formula [D-3], D 3 represents an alkyl group having 1 to 4 carbon atoms. The reaction can be carried out at any concentration, preferably 1-50% by mass, more preferably 5-30% by mass. The reaction is initially carried out at a high concentration, and solvent may be added subsequently. During the reaction, the ratio of the total moles of the diamine components to the total moles of the tetracarboxylic acid components is preferably 0.8-1.2. Similar to typical polycondensation reactions, the closer this mole ratio is to 1.0, the larger the molecular weight of the resulting polyamide becomes.

[0062] The polyacrylic acid obtained from the above reaction can be recovered by injecting it into a poor solvent while the reaction solution is being thoroughly stirred, causing the polyacrylic acid to precipitate. This precipitation process can be repeated several times, followed by washing with the poor solvent and drying at room temperature or by heating, thereby obtaining refined polyacrylic acid powder. The poor solvent is not particularly limited and examples include water, methanol, ethanol, hexane, butylcerox, acetone, and toluene.

[0063] When the polyimide precursor is a polyamide ester (a polyamide precursor having at least one of the repeating units represented by formula (a) in which R is a monovalent organic group), it can be manufactured by known methods such as (1) esterification of polyamide obtained from tetracarboxylic dianhydride and diamine, (2) reaction of tetracarboxylic diester dichloride with diamine, and (3) polycondensation of tetracarboxylic diester and diamine.

[0064] [End-capping agent] In the synthesis of polymer (A) in this invention, a tetracarboxylic acid component containing tetracarboxylic acid dianhydride or its derivative, a diamine component, and, depending on the circumstances, a diisocyanate compound, can be synthesized together with an appropriate end-capping agent to form an end-sealed polymer.

[0065] End-capping agents, such as: acetic anhydride, maleic anhydride, naphthalic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride, etc.; dibutyl dicarbonate, diallyl dicarbonate, etc.; chlorocarbonyl compounds such as acrylonitrile chloride, methacrylamide chloride, nicotinic acid chloride; aniline, Monoamine compounds such as 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate; and isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate.

[0066] The proportion of the capping agent used is preferably 20 mol or less, and more preferably 10 mol or less, relative to the total of 100 mol of the diamine and, if necessary, the organic diol used. The proportion of the capping agent used is preferably 0.01 mol or more, and more preferably 0.1 mol or more, relative to the total of 100 mol of the diamine used.

[0067] Furthermore, polyimide can be obtained by cyclizing (nitroimidizing) the polyimide precursor (A) of polymer (A). Also, the nitroimidization rate referred to in this specification is the ratio of nitroimide groups to the total amount of nitroimide groups and carboxyl groups (or their derivatives) derived from tetracarboxylic dianhydride or its derivatives. The nitroimidization rate does not necessarily have to be 100% and can be adjusted arbitrarily according to the application and purpose.

[0068] Methods for amide imidizing polyimide precursors include thermal amide imidization, which involves directly heating a solution of the polyimide precursor, and catalytic amide imidization, which involves adding a catalyst to a solution of the polyimide precursor.

[0069] The preferred temperature for thermal acetamidization of the polyimide precursor in solution is 100~400℃, more preferably 120~250℃, and it is preferable to drain the water generated by the acetamidization reaction outside the system during the process.

[0070] Catalytic amide formation of polyimide precursors can be carried out by adding an alkaline catalyst and an acid anhydride to a solution of the polyimide precursor, preferably at -20 to 250°C, more preferably at 0 to 180°C with stirring. The amount of alkaline catalyst is preferably 0.5 to 30 mol / L of the amide group, more preferably 2 to 20 mol / L, and the amount of acid anhydride is preferably 1 to 50 mol / L of the amide group, more preferably 3 to 30 mol / L. Examples of alkaline catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among these, pyridine is ideal because it has a moderate alkalinity that facilitates the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and phenylmethyltetrahydroquinone. Acetic anhydride is ideal because it facilitates purification after the reaction. The amide ratio achieved by catalytic amide imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0071] When recovering polyimide precursors or polyimide from a reaction solution of polyimide precursors or polyimide, the reaction solution can be added to a solvent to precipitate it. Solvents used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylceryl ketone, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer obtained after precipitation is filtered and then dried at room temperature or under reduced pressure, or by heating. Furthermore, repeating the process of redissolving the precipitated polymer in an organic solvent and then precipitating it again, for example, 2 to 10 times, can reduce impurities in the polymer. Solvents used in this process include, for example, alcohols, ketones, or hydrocarbons. Using three or more solvents selected from these sources will result in higher purification efficiency, which is ideal.

[0072] The molecular weight of the polymer (A) used in this invention, when considering the strength, workability and coating properties of the liquid crystal alignment film obtained from it, is preferably 5,000 to 1,000,000 by weight average molecular weight as determined by GPC (Gel Permeation Chromatography), and more preferably 10,000 to 150,000.

[0073] <Manufacturing of Polyester (B)> The aforementioned polyester (B) can be obtained, for example, by reacting a component (o) containing an organic diol having two hydroxyl groups within its molecule with a component (c) containing a tetracarboxylic acid dianhydride or a derivative thereof having a tetravalent organic group represented by Xar within its molecule. Here, the aforementioned component (o) contains an organic diol (o) having a substructure represented by the following formula (EG) within its molecule. [Chemistry 29] n is an integer greater than or equal to 5. R represents a hydrogen atom or a methyl group.

[0074] Furthermore, when the above polyester (B) contains the repeating unit represented by the above formula (b2), it can be obtained by reacting (i) component, which contains a compound having two isocyanate groups in its molecule, in addition to the above monomer component.

[0075] Components (o), (c), and (i) as needed may each be one or more.

[0076] Organic diols (o), for example: the organic diols represented by the repeating unit in formula (b1) above, can be listed as diol compounds represented by "HEH" (E and E in formula (b1) are synonymous.).

[0077] Furthermore, when using a diol (o') that does not contain the substructure represented by the above formula (EG), the monomer component used to obtain the above polyester (B) contains the above diol (o').

[0078] (i) The component, for example: O=C=NA 1-N=C=O (A 1 is the same as A 1 in formula (b2)). represents a diisocyanate compound.

[0079] The reactions of components (o), (c), and (i) as needed are typically carried out in an organic solvent. There are no particular restrictions on the organic solvent used, as long as it dissolves the resulting polyester (B). Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidineone, N-methyl-ε-caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, triammonium hexamethylphosphate, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl ketone, methyl isopropyl ketone, and methyl cyprothiophene. Ethyl cerroxo, methyl cerroxo acetate, ethyl cerroxo acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, di... Propylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dimethylethane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl carbonate, Propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, dimethyl ether, or 4-hydroxy-4-methyl-2-pentanone, etc. These can be used alone or in combination. Furthermore, even solvents insoluble in polyester (B) can be mixed with the above solvents. Also, moisture in organic solvents can hinder the polymerization reaction, so it is best to dehydrate and dry the organic solvents used.

[0080] In the method for synthesizing the polyester (B) obtained by reacting component (o) and component (c) used in this invention, the blending amounts of component (o) and component (c) are preferably such that the ratio (component (am) / hydroxyl) of the total number of hydroxyl groups and the total number of acetic acid groups or their derivatives possessed by tetracarboxylic dianhydride (hereinafter also referred to as am) is preferably 0.8 to 1.2 or less, more preferably 0.9 to 1.2 or less, and even more preferably 0.9 to 1.1 or less, is obtained by reacting the components in an organic solvent.

[0081] Furthermore, regarding the monomer components of the aforementioned polyester (B), when the aforementioned component (i) is present, in the method for synthesizing the polyester (B) obtained by reacting component (o) with component (c) and component (i), it is preferable to react the components (o), (i), and (c) in an organic solvent such that the ratio of the number of hydroxyl groups, the number of isocyanate groups, and the total number of groups (am) ((isocyanate groups + groups (am)) / hydroxyl groups) is preferably 0.8 to 1.2 or less, more preferably 0.9 to 1.2 or less, and even more preferably 0.9 to 1.1 or less.

[0082] Furthermore, when using two or more organic diols, the reaction of the diisocyanate compound or tetracarboxylic dianhydride or its derivatives can be carried out after mixing the two or more organic diols, or the individual organic diols can react with the diisocyanate compound or tetracarboxylic dianhydride or its derivatives separately. Alternatively, after reacting the organic diol with the diisocyanate compound or tetracarboxylic dianhydride or its derivatives, the resulting terminal isocyanate compound or acetic acid terminal or its derivative can be reacted with other organic diol compounds, and then reacted with the diisocyanate compound or tetracarboxylic dianhydride or its derivatives. The same applies when using two or more diisocyanate compounds or tetracarboxylic dianhydride or its derivatives. The desired polyester (B) can be manufactured in this manner.

[0083] The reaction temperature for components (o), (c), and (i) (if applicable) is preferably set at 0–160°C, more preferably 10–150°C. The reaction time can be appropriately selected depending on the scale of the reaction and the reaction conditions used. Furthermore, if necessary, the reaction can also be carried out in the presence of catalysts such as tertiary amines, alkali metals, alkaline earth metals, tin, zinc, titanium, cobalt, or other metal or semi-metal compounds. The total concentration of components (o) and (i) in the reaction solution is preferably 1–50% by mass, more preferably 5–30% by mass. The reaction is initially carried out at a high concentration, and organic solvents may be added subsequently.

[0084] The molecular weight of the polyester (B) used in this invention, when considering the strength, workability and coating properties of the liquid crystal alignment film obtained from it, is preferably 4,000 to 80,000 by weight average molecular weight as determined by GPC (Gel Permeation Chromatography), and more preferably 6,000 to 60,000. The polyester used in this invention has a viscosity of 10~5,000 mPa·s at 25°C, which is more preferably 100~3,000 mPa·s. Furthermore, the above viscosity values ​​are ideal values ​​for a solid component concentration in the polyester solution ranging from 10 to 50% by mass. If the viscosity is within the above range, it is more ideal from the perspective of achieving the desired effect of the present invention. The above viscosity was measured using a TVE-22H E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, using a conical rotor TE-1 (1°34', R24) at a temperature of 25°C.

[0085] The polymer composition of the present invention may also contain polymers other than polymer (A) and polyester (B). Specific examples of other polymers include those selected from the group consisting of polyesters other than polyester (B), polysiloxanes, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley), GSM301 (manufactured by GIFUSHELLAC), etc.; specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAM-600 (manufactured by Kuraray); and specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP JAPAN). Other polymers may be used alone or in combination of two or more. Ideally, the proportion of other polymers relative to the total number of polymers in the polymer composition should be less than 90 parts by mass, 10-90 parts by mass is better, and 20-80 parts by mass is even better.

[0086] The polymer composition of the present invention is preferably a liquid composition in which the above-mentioned polymer (A) and polyester (B) are dissolved or dispersed in an organic solvent. Specifically, the organic solvent contained in the above-mentioned polymer composition is not particularly limited as long as the polymer components can be uniformly dissolved, and examples include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylpropionic acid, tetramethylurea, N,N-diethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinedione, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 3-methoxy-N,N - Dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-3-methoxypropyl-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (these are also collectively referred to as "good solvents"). Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, or γ-butyrolactone are preferred. The content of good solvent is preferably 20-99% by mass of the total solvent contained in the polymer composition, 20-90% by mass is even better, and 30-80% by mass is even more ideal. The total content of polymer (A) and polyester (B) used in this invention is preferably 1 to 100 parts by mass relative to 100 parts by mass of the total polymer contained in the liquid crystal alignment agent, more preferably 10 to 100 parts by mass, and even more preferably 20 to 100 parts by mass. Furthermore, the total content of the aforementioned polymer (A) and polyester (B) may be 90 parts by mass or less, or 80 parts by mass or less, relative to 100 parts by mass of the total polymer contained in the liquid crystal alignment agent.

[0087] Furthermore, for the organic solvents contained in the polymer composition, it is preferable to use a mixed solvent that, in addition to the solvents mentioned above, also incorporates solvents that improve the coatability and surface smoothness of the coating film when applying the polymer composition (also known as undesirable solvents). Specific examples of undesirable solvents used are as follows, but are not limited to these solvents. The content of undesirable solvents is ideally 1-80% by mass of the total solvents contained in the polymer composition, 10-80% by mass is better, and 20-70% by mass is especially preferred. The type and content of undesirable solvents can be appropriately selected according to the coating equipment, coating conditions, coating environment, etc. of the polymer composition.

[0088] Unsuitable solvents include: diisopropyl ether, diisobutyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propyl carbonate, ethyl carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl ether, ethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)- 1-Propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc.

[0089] Among them, diisobutylmethanol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone are preferred.

[0090] An ideal solvent combination of good and bad solvents can be listed as follows: N-methyl-2-pyrrolidone with ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone with γ-butyrolactone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone with γ-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone with propylene glycol diacetate; N,N-dimethyllactamine with diisobutyl ketone; N-methyl-2-pyrrolidone with ethyl 3-ethoxypropionate; N-ethyl-2-pyrrolidone with ethyl 3-ethoxypropionate; N-methyl-2-pyrrolidone with ethyl 3-ethoxypropionate and dipropylene glycol monomethyl ether; N... N-methyl-2-pyrrolidone with ethyl 3-ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone with ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether, N-ethyl-2-pyrrolidone with ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether, N-methyl-2-pyrrolidone with ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone with dipropylene glycol dimethyl ether, N,N-dimethyllactamine with ethylene glycol monobutyl ether, N,N-dimethyllactamine with propylene glycol diacetate, N-ethyl-2-pyrrolidone with diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone with diethylene glycol monoethyl ether and butylceroxose acetate, N-methyl-2-pyrrolidone with diethylene glycol monomethyl ether and butylceroxose acetate, N,N-Dimethyllactic acid with diethylene glycol diethyl ether, N-methyl-2-pyrrolidone with γ-butyrolactone with 4-hydroxy-4-methyl-2-pentanone with diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone with N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with propylene glycol monobutyl ether, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with diisobutyl ketone, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with propylene glycol monobutyl ether, N-methyl-2-pyrrolidone with 4-hydroxy- 4-Methyl-2-pentanone with ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with propylene glycol diacetate, N-ethyl-2-pyrrolidone with 4-hydroxy-4-methyl-2-pentanone with dipropylene glycol dimethyl ether, γ-butyrolactone with 4-hydroxy-4-methyl-2-pentanone with diisobutyl ketone, γ-butyrolactone with 4-hydroxy-4-methyl-2-pentanone with propylene glycol diacetate, N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether with diisobutyl ketone, N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether with diisopropyl ether, N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether with diisobutylmethanol, N-methyl-2-pyrrolidone with γ- Butyrolactone with dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone with propylene glycol monobutyl ether with dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether with dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone with diethylene glycol diethyl ether with dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether with propylene glycol diacetate, N-ethyl-2-pyrrolidone with propylene glycol monobutyl ether with diisobutyl ketone, N-ethyl-2-pyrrolidone with γ-butyrolactone with diisobutyl ketone, N-ethyl-2-pyrrolidone with N,N-dimethyllactamine with diisobutyl ketone, N-methyl-2-pyrrolidone with ethylene glycol monobutyl ether with ethylene glycol monobutyl ether acetate, γ-butyrolactone with ethylene glycol monobutyl ether acetate with dipropylene glycol dimethyl ether Ethers, N-ethyl-2-pyrrolidone with ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone with 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone with cyclohexyl acetate and diacetone alcohol, N,N-dimethylpropionic acid with 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylpropionic acid with propylene glycol diacetate, tetramethylurea with 4-hydroxy-4-methyl-2-pentanone, tetramethylurea with propylene glycol diacetate, N,N-dimethylpropionic acid with propylene glycol monobutyl ether, tetramethylurea with propylene glycol monobutyl ether, tetramethylurea with cyclohexanone and propylene glycol monomethyl ether, N,N-dimethylpropionic acid with propylene glycol monomethyl ether, N,N-dimethylpropionic acid with ethylene glycol monobutyl ether acetate, N,N-Dimethylpropionic acid with ethylene glycol monobutyl ether, tetramethylurea with propylene glycol monomethyl ether, N,N-dimethylpropionic acid with cyclohexanone with diethylene glycol diethyl ether, N,N-diethylmethionic acid with propylene glycol monomethyl ether, N,N-diethylmethionic acid with 4-hydroxy-4-methyl-2-pentanone, N,N-diethylmethionic acid with propylene glycol monomethyl ether, cyclohexanone with propylene glycol monomethyl ether, cyclopentanone with propylene glycol monomethyl ether, N-methyl-2-pyrrolidone with cyclohexanone with propylene glycol monomethyl ether, etc.

[0091] The polymer composition of the present invention may also additionally contain components other than polymer components and organic solvents (hereinafter also referred to as additive components). These additive components include, for example: crosslinking compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds used to adjust the dielectric constant and resistance of the resin film. The aforementioned crosslinking compound is, for example, selected from at least one crosslinking compound (c-1) having at least one substituent selected from epoxy group, isocyanate group, glycidyl group, cyclic carbonate group, capped isocyanate group, hydroxyl group and alkoxy group, and crosslinking compound (c-2) having polymerizable unsaturated group. By using the aforementioned cross-linking compounds, it is also possible to obtain a liquid crystal display element that reduces flickering and other phenomena that occur when backlight illuminates the liquid crystal display element during initial liquid crystal operation.

[0092] Ideal examples of the aforementioned cross-linking compounds (c-1) and (c-2) can be listed below. Compounds containing epoxy groups (c-1) can be listed as follows: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, bisphenol A type epoxy resins such as EPIKOTE 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins such as EPIKOTE 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenol A type epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). Epoxy resins containing a biphenyl backbone, such as YX6954BH30 (manufactured by Mitsubishi Chemical Co., Ltd.); phenolic resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.); (o-, m-, and p-)cresol phenolic resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.); tetra(epoxypropoxymethyl)methane; N,N,N',N'-tetracyclooxypropyl-1,4-phenylenediamine; N,N,N',N'-tetracyclooxypropyl-2,2'-dimethyl-4,4'-diaminobiphenyl; 2,2-bis[4-(N,N-dicyclooxypropyl-4-aminophenoxy)phenyl]propane; N,N,N',N'-tetracyclooxypropyl-1,4-phenylenediamine; Compounds containing tertiary nitrogen atoms and aromatic carbon atoms, such as propyl-4,4'-diaminodiphenylmethane; N,N,N',N'-tetracyclooxypropyl-1,2-diaminocyclohexane, N,N,N',N'-tetracyclooxypropyl-1,3-diaminocyclohexane, N,N,N',N'-tetracyclooxypropyl-1,4-diaminocyclohexane, bis(N,N-dicyclooxypropyl-4-aminocyclohexyl)methane, bis(N,N-dicyclooxypropyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-dicyclooxypropyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-dicyclooxypropylaminomethyl)cyclohexane, 1 Compounds containing tertiary nitrogen atoms and aliphatic carbon atoms bonded by tertiary nitrogen atoms and aliphatic carbon atoms, such as 4-bis(N,N-dicyclooxypropylaminomethyl)cyclohexane, 1,3-bis(N,N-dicyclooxypropylaminomethyl)benzene, 1,4-bis(N,N-dicyclooxypropylaminomethyl)benzene, 1,3,5-tris(N,N-dicyclooxypropylaminomethyl)cyclohexane, 1,3,5-tris(N,N-dicyclooxypropylaminomethyl)benzene, isocyanurate compounds such as tricyclooxypropyl isocyanate produced by Nissan Chemical Co., Ltd., compounds described in paragraph

[0037] of Japanese Patent Application Publication No. 10-338880, and compounds described in WO2017 / 170483, etc.; Compounds containing an isocyanate group include the aforementioned diisocyanate compounds, etc. Compounds containing propylene oxide (c-1) include 1,4-bis{[(3-ethyl-3-epoxypropane)methoxy]methyl}benzene (ARON OXETANE OXT-121(XDO)), di[2-(3-epoxypropane)butyl] ether (ARON OXETANE OXT-221(DOX)), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), and compounds containing two or more propylene oxide alkyl groups as described in paragraphs

[0170] to

[0175] of WO2011 / 132751, etc. Compounds having a cyclic carbonate group (c-1) include N,N,N',N'-tetra[(2-sideoxy-1,3-dioxolane-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N'-bis[(2-sideoxy-1,3-dioxolane-4-yl)methyl]-1,3-phenylenediamine, and compounds described in WO2011 / 155577, etc. Compounds having capped isocyanate groups include CORONATEAP STABLE M, CORONATE2503, 2515, 2507, 2513, 2555, MILLIONATEMS-50 (all manufactured by Tosoh Corporation), TAKENATEB-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals Corporation), compounds having two or more protected isocyanate groups as described in paragraphs

[0046] to

[0047] of Japanese Patent Application Publication No. 2014-224978, and compounds having three or more protected isocyanate groups as described in paragraphs

[0119] to

[0120] of WO2015 / 141598, etc. Compounds having hydroxyl and / or alkoxy groups (c-1) include N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamine, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compounds described in paragraph

[0058] of International Publication No. 2015 / 072554, Japanese Patent Application Publication No. 2016-118753, compounds described in Japanese Patent Application Publication No. 2016-200798, and compounds described in WO2010 / 074269, etc.; Crosslinked compounds (c-2) with polymerizable unsaturated groups include glycerol mono(meth)acrylate, glycerol di(meth)acrylate (a mixture of 1,2- and 1,3-dimethyl acrylates), glycerol tri(meth)acrylate, glycerol 1,3-diglyceric acid di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, etc.

[0093] Among the aforementioned crosslinking compounds (c-1) and (c-2), N,N,N',N'-tetracyclooxypropylmethylenediamine, 1,3-bis(N,N-dicyclooxypropylaminomethyl)cyclohexane, N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, TAKENATEB-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B- 882N, 1,3,5-tris(2-hydroxyethyl)isocyanurate, trichloropropyl isocyanurate, N,N,N',N'-tetra(2-hydroxyethyl)hexamethylenediamine, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane are preferred.

[0094] The above are examples of crosslinking compounds, and are not limited to these. Furthermore, the crosslinking compounds used in the polymer compositions of the present invention may be one type or a combination of two or more. In the polymer composition of the present invention, the content of the crosslinking compound is 0.1 to 150 parts by mass, or 0.1 to 100 parts by mass, or 1 to 50 parts by mass relative to 100 parts by mass of all polymer components.

[0095] The compounds used to adjust the dielectric constant and resistance of the resin film include, for example, monoamines such as 3-pyridinemethylamine, which are aromatic heterocyclic compounds containing nitrogen atoms. When using a monoamine with an aromatic heterocyclic compound containing nitrogen, it is preferable to use 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component in the polymer composition, and more preferably 0.1 to 20 parts by mass.

[0096] Ideal examples of functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-epoxypropoxypropylmethyldimethoxysilane. Alkane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. When using functional silane compounds, it is preferable that the amount used is 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the polymer composition, and more preferably 0.1 to 20 parts by mass.

[0097] The concentration of solid components in the polymer composition (the proportion of the total mass of components other than the solvent in the polymer composition to the total mass of the polymer composition) can be appropriately selected considering factors such as viscosity and volatility, and is preferably in the range of 1 to 10% by mass. That is, the polymer composition is coated on the substrate surface as described later, preferably by heating, to form a resin film.

[0098] The ideal range of solid content concentration depends on the method used to coat the polymer composition onto the substrate. For example, when using spin coating, a solid content concentration of 1.5 to 4.5% by mass is preferred. When using printing, a solid content concentration of 3 to 9% by mass is preferred, thereby achieving a solution viscosity of 12 to 50 mPa·s. When using inkjet printing, a solid content concentration of 1 to 5% by mass is preferred, thereby achieving a solution viscosity of 3 to 15 mPa·s. The preferred temperature for preparing the polymer composition is 10 to 50°C, more preferably 20 to 30°C.

[0099] <Applications and Resin Films> The polymer composition described above, for example, can form a resin film by coating it onto a substrate, preferably by evaporating the solvent components through heat treatment. The polymer composition and resin film of this invention are effectively applicable to various technical applications, such as liquid crystal alignment agents, electronic circuit materials, semiconductor materials, electrical insulation materials, wire coating materials, lighting applications, molding materials, and so on. Specifically, it is applicable to various resin films used in display elements, semiconductor elements, actuators such as motors, piezoelectric sensors, pyroelectric sensors, and other types of sensors. Examples include liquid crystal alignment films (liquid crystal alignment films for phase difference films, liquid crystal alignment films for scanning antennas, liquid crystal array antennas, or liquid crystal alignment films for transmission-scattering type liquid crystal dimming elements), protective films (e.g., protective films for color filters), spacer films, interlayer insulating films, anti-reflective films, wiring coating films, antistatic films, and motor insulating films (gate insulating films for flexible displays). Among these, the polymer composition of this invention is ideally suited for use as a liquid crystal alignment agent.

[0100] <Liquid crystal alignment agent> The liquid crystal alignment agent of this invention is composed of the polymer composition of this invention. That is, the liquid crystal alignment agent of this invention, like the polymer composition, contains the aforementioned polymer (A) and polyester (B). Furthermore, it is preferable to contain at least one of other polymers, organic solvents, and additives. Detailed information regarding specific examples, blending ratios, and solid content concentrations of the aforementioned polymer (A), polyester (B), other polymers, organic solvents, and additives can be found in the description of the aforementioned polymer composition.

[0101] [Liquid crystal alignment film and liquid crystal display element] By using the aforementioned polymer composition or liquid crystal alignment agent, a liquid crystal alignment film as a resin film can be manufactured. Furthermore, the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the aforementioned polymer composition or liquid crystal alignment agent. The operating mode of the liquid crystal display element of the present invention is not particularly limited; for example, it can be applied to various operating modes such as TN type, STN (Super Twisted Nematic) type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type), FFS type, and optically compensated bending type (OCB type).

[0102] The liquid crystal display element of the present invention can be manufactured by, for example, a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), a method including steps (1) to (3), (4-2) and (4-4), or a method including steps (1) to (3), (4-3) and (4-4).

[0103] <Step (1): The step of coating the liquid crystal alignment agent on the substrate> Step (1) is the step of coating the liquid crystal alignment agent of the present invention onto the substrate. A specific example of step (1) is as follows. On one side of a substrate having a patterned transparent conductive film, the liquid crystal alignment agent of the present invention is applied using a suitable coating method such as roll coating, spin coating, printing, or inkjet coating. Here, the substrate is not particularly limited to any substrate with high transparency; glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and other plastic substrates can also be used. Furthermore, for reflective liquid crystal display elements, if only a single-sided substrate is used, opaque materials such as silicon wafers can be used; in this case, the electrodes can also be made of light-reflecting materials such as aluminum. Moreover, when manufacturing IPS or FFS type liquid crystal display elements, a substrate having electrodes composed of a patterned comb-shaped transparent conductive film or metal film is used, along with a facing substrate without electrodes.

[0104] Methods for coating liquid crystal alignment agents onto a substrate and forming a film include screen printing, offset printing, flexographic printing, inkjet printing, and spraying. Among these, inkjet printing is an ideal method for coating and forming a film.

[0105] <Step (2): Calcination of the coated liquid crystal alignment agent> Step (2) is the step of calcining the liquid crystal alignment agent that has been coated on the substrate to form a film. A specific example of step (2) is as follows. After coating the liquid crystal alignment agent onto the substrate in step (1), a heating method such as a hot plate, a thermally circulating oven, or an IR (infrared) oven can be used to evaporate the solvent or perform thermal amide formation of polyamide or polyamide ester. The drying and calcination steps after coating the liquid crystal alignment agent of this invention can be performed at any temperature and for any time, and can be repeated multiple times. To reduce the solvent temperature of the liquid crystal alignment agent, for example, it can be performed at 40~180°C. Considering the need for cost reduction, it can be performed at 40~150°C. The calcination time is not particularly limited, and can be 1~10 minutes or 1~5 minutes. When performing thermal amide formation of polyamide or polyamide ester, a calcination step at a temperature range of, for example, 150~300°C or 150~250°C can be added after the above steps. The calcination time is not specifically limited; examples include calcination times of 5-40 minutes or 5-30 minutes. If the film after calcination is too thin, the reliability of the liquid crystal display element will be reduced. Therefore, 5~300nm is more ideal, and 10~200nm is even more ideal.

[0106] <Step (3): The step of performing alignment treatment on the membrane obtained in step (2)> Step (3) involves performing alignment treatment on the film obtained in step (2), depending on the circumstances. That is, in horizontally aligned liquid crystal display elements such as IPS or FFS types, the coating is subjected to alignment capability imparting treatment. On the other hand, in vertically aligned liquid crystal display elements such as VA or PSA types, the formed coating can be directly used as a liquid crystal alignment film, but alignment capability imparting treatment can also be performed on the coating. Alignment treatment methods for liquid crystal alignment films include rubbing treatment and photoalignment treatment. For photoalignment treatment, a method can be used where the surface of the film is irradiated with radiation deflected in a certain direction, and, depending on the circumstances, heated to impart liquid crystal alignment properties (also called liquid crystal alignment capability). The radiation can be ultraviolet light or visible light with a wavelength of 100-800 nm. Preferably, it is ultraviolet light with a wavelength of 100-400 nm, more preferably 200-400 nm.

[0107] The radiation dose is preferably 1 to 10,000 mJ / cm², with 100 to 5,000 mJ / cm² being more preferred. Furthermore, to improve liquid crystal alignment during irradiation, the substrate with the film can be heated at 50 to 250°C while being irradiated. The liquid crystal alignment film prepared in this manner enables the liquid crystal molecules to be stably aligned in a specific direction. Alternatively, the liquid crystal alignment film irradiated with polarized radiation as described above can be contacted with water or solvent, or the irradiated liquid crystal alignment film can be heated.

[0108] The solvents used in the above-mentioned contact treatment are not particularly limited as long as they can dissolve the decomposition products generated from the film due to radiation irradiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl ceroxysulfate, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among these, considering versatility and solvent safety, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate are more ideal, with water and 1-methoxy-2-propanol or ethyl lactate being even more ideal. One solvent or a combination of two or more solvents can be used.

[0109] The preferred temperature for heat treatment of the above-mentioned radiation-irradiated coating is 50~300℃, and even more preferably 120~250℃. The preferred heat treatment time is 1~30 minutes.

[0110] <Step (4): Steps for fabricating liquid crystal cells> Prepare two substrates with liquid crystal alignment films formed as described above, and place liquid crystal between the two opposing substrates. Specifically, the following two methods can be listed. The first method involves aligning two substrates with their respective liquid crystal alignment films facing each other, separated by a cell gap. Then, the peripheries of the two substrates are bonded together using a sealant, and liquid crystal composition is injected into the cell gaps separated by the substrate surface and the sealant. After the liquid crystal composition contacts the film surface, the injection hole is sealed. There are no special restrictions on the liquid crystal composition mentioned above; various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. Furthermore, liquid crystal compositions with positive dielectric anisotropy will be referred to as positive liquid crystals, and liquid crystal compositions with negative dielectric anisotropy will be referred to as negative liquid crystals. The aforementioned liquid crystal composition may also contain liquid crystal compounds having fluorine atoms, hydroxyl groups, amino groups, fluorine-containing groups (e.g., trifluoromethyl), cyano groups, alkyl groups, alkoxy groups, alkenyl groups, isothiocyanate groups, heterocyclic groups, cycloalkanes, cycloalkenes, steroid skeletons, benzene rings, or naphthyl rings. It may also contain compounds with two or more rigid sites (liquid crystal proto-skeletons) exhibiting liquid crystal properties within the molecule (e.g., rigid biphenyl structures, or biphenyl structures linked by alkyl groups forming a double liquid crystal proto-skeleton). The liquid crystal composition may also be a nematic phase liquid crystal composition, a lamellar phase liquid crystal composition, or a cholesterol phase liquid crystal composition. Furthermore, in view of improving the alignment properties of the liquid crystal, additives can be added to the aforementioned liquid crystal composition. Such additives include photopolymerizable monomers such as compounds with polymerizable groups (such as methacrylic acid groups); optically active compounds (e.g., S-811 manufactured by Merck); antioxidants; ultraviolet absorbers; pigments; defoamers; polymerization initiators or polymerization inhibitors, etc. Positive LCDs include those manufactured by Merck such as ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081. Negative liquid crystal displays include MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, and MLC-7029 manufactured by Merck. Furthermore, in the PSA mode, an example of a liquid crystal containing a compound with polymerizable groups is MLC-3023 manufactured by Merck.

[0111] The second method is called the ODF (One Drop Fill) method. On one of the two substrates with a pre-formed liquid crystal alignment film, a UV-curable sealant is applied to a predetermined location. Then, liquid crystal composition is dropped onto several predetermined locations on the liquid crystal alignment film surface. Next, the other substrate is bonded with the liquid crystal alignment films facing each other, pressing the liquid crystal composition onto the entire surface of the substrate so that it contacts the film surface. Then, the entire surface of the substrate is irradiated with UV light to harden the sealant. When using either method, it is advisable to further heat until the liquid crystal composition becomes isotropic, and then slowly cool it to room temperature to remove the flow alignment during liquid crystal filling. Furthermore, when the coating is subjected to friction treatment, the two substrates are arranged facing each other at a predetermined angle, such as orthogonal or antiparallel, with the friction directions of each coating film being opposite each other. For sealants, epoxy resins containing alumina spheres can be used as hardeners and spacers. For liquid crystals, nematic liquid crystals and smectic liquid crystals are examples, with nematic liquid crystals being preferred.

[0112] The liquid crystal alignment agent of the present invention is also suitable for use in liquid crystal display elements (PSA type liquid crystal display elements) that have a liquid crystal layer between a pair of substrates having electrodes, and a liquid crystal composition containing a polymerizable compound that can polymerize by at least one of active energy rays and heat disposed between the pair of substrates, and polymerize the polymerizable compound by applying voltage between the electrodes and irradiating with active energy rays and heating. Furthermore, the liquid crystal alignment agent of the present invention is also suitable for use in liquid crystal display elements (SC-PVA type liquid crystal display elements) manufactured by applying a voltage between electrodes, wherein a liquid crystal layer is provided between a pair of substrates having an electrode, and a liquid crystal alignment film containing polymerizable groups that can polymerize due to at least one of active energy rays and heat is disposed between the pair of substrates.

[0113] <Step (4-2): Case of PSA type liquid crystal display element> Except for injecting or dropping the liquid crystal composition containing the polymeric compound, the process is the same as described in (4) above. Examples of polymeric compounds include polymeric compounds having one or more polymeric unsaturated groups such as acrylate groups or methacrylate groups within their molecules.

[0114] Step (4-3): The situation of SC-PVA mode liquid crystal display element Alternatively, a liquid crystal display element can be manufactured by performing the same procedure as described above (4), followed by the ultraviolet irradiation step described later. Using this method, a liquid crystal display element with excellent response speed can be obtained with a small amount of light irradiation, similar to the manufacturing of the PSA-type liquid crystal display element described above. The compound having a polymerizable group can be a compound having one or more of the aforementioned polymerizable unsaturated groups within its molecule, and its content relative to 100 parts by mass of the total polymer component is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass. Furthermore, the aforementioned polymerizable group can be present in the polymer used as a liquid crystal alignment agent. Examples of such polymers include polymers obtained by using a diamine component containing a diamine terminally having the aforementioned photopolymerizable group in a reaction.

[0115] Step (4-4): Steps for irradiating with ultraviolet light The liquid crystal cells are irradiated with a voltage applied between the conductive films on the substrate as obtained in either (4-2) or (4-3) above. The applied voltage can be, for example, DC or AC of 5-50V. The irradiated light can be ultraviolet light or visible light containing wavelengths of, for example, 150-800nm, but ultraviolet light containing wavelengths of 300-400nm is preferred. The light source can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonant lamp, a xenon lamp, or an excimer laser. The irradiation intensity is preferably 1,000-200,000 J / m², more preferably 1,000-100,000 J / m².

[0116] Furthermore, a polarizing plate can be attached to the outer surface of the liquid crystal cell as needed to obtain a liquid crystal display element. Examples of polarizing plates attached to the outer surface of the liquid crystal cell include: a polarizing film called an "H film" that has polyvinyl alcohol extended and aligned on one side and absorbs iodine on the other side, which is sandwiched with a cellulose acetate protective film to obtain a polarizing plate, or a polarizing plate composed of the H film itself.

[0117] The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable game consoles, word processors, laptops, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, and various display devices such as monitors, LCD TVs, and message displays. [Example]

[0118] The following examples illustrate the invention in more detail, but the invention is not limited to these examples. Furthermore, the abbreviations for compounds and solvents are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone GBL: γ-Butyrolactone BCS: Ethylene glycol monobutyl ether (Diamine) DA-1~DA-3: Each is a compound represented by the formula (DA-1)~(DA-3). (Tetracarboxylic acid dianhydride) CA-1~CA-2: Each is a compound represented by the formula (CA-1)~(CA-2). (Diisocyanate) DI-1:4,4'-Diphenylmethane diisocyanate (diol) EG-1: Polyethylene Glycol 600 (manufactured by Tokyo Chemical Industry Co., Ltd.) (additive) AD-1: Compounds represented by the formula (AD-1) [Chemistry 30] [Chemistry 31] [Chemistry 32]

[0119] <Viscosity> In the synthesis example, the viscosity of the polymer solution was measured using a TVE-22H E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL, a conical rotor TE-1 (1°34', R24), and a temperature of 25°C.

[0120] [Polymer Synthesis] (Synthesis example 1) DA-1 (4.81 g, 16.8 mmol), DA-3 (1.25 g, 4.20 mmol), NMP (27.3 g), and GBL (27.3 g) were measured into a 100 mL flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred while supplying nitrogen gas until dissolved. While stirring this diamine solution under water cooling, CA-1 (3.83 g, 19.5 mmol), NMP (17.2 g), and GBL (17.2 g) were added. The mixture was stirred under nitrogen for 2 hours to obtain a polyacrylic acid solution (PAA-1) (viscosity: 108 mPa·s). (Synthesis example 2) Measure DA-1 (3.15 g, 11.0 mmol), DA-2 (2.69 g, 11.0 mmol), NMP (26.3 g), and GBL (26.3 g) into a 100 mL flask equipped with a stirrer and a nitrogen inlet tube, and dissolve them by stirring while introducing nitrogen. While stirring this diamine solution under water cooling, add CA-1 (4.01 g, 20.5 mmol), NMP (18.1 g), and GBL (18.1 g), and stir for 2 hours under nitrogen to obtain a polyacrylic acid solution (PAA-2) (viscosity: 119 mPa·s). (Synthesis example 3) EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g), and GBL (11.3 g) were measured into a 100 mL round-bottom flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred while supplying nitrogen to dissolve the EG-1. While stirring this diamine solution under water cooling, CA-2 (4.09 g, 18.8 mmol), NMP (3.07 g), and GBL (3.07 g) were added. The mixture was stirred at 70 °C for 20 hours under nitrogen. Then, DI-1 (1.38 g, 5.50 mmol), NMP (1.03 g), and GBL (1.03 g) were added. The mixture was stirred at 23 °C for 6 hours under nitrogen to obtain a polymer solution (viscosity: 423 mPa·s). Take 5.0 g of the polymer solution obtained above into a 30 mL Erlenmeyer flask equipped with a stir bar, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-1). (Synthesis Example 4) EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g), and GBL (11.3 g) were measured into a 100 mL round-bottom flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred while supplying nitrogen to dissolve the diamine solution. While stirring this diamine solution under water cooling, CA-2 (2.73 g, 12.5 mmol), NMP (2.04 g), and GBL (2.04 g) were added. The mixture was stirred at 70°C for 20 hours under nitrogen. Then, DI-1 (2.94 g, 11.8 mmol), NMP (1.03 g), and GBL (1.03 g) were added. The mixture was stirred at 23°C for 6 hours under nitrogen to obtain a polymer solution (viscosity: 520 mPa·s). Take 5.0 g of the polymer solution obtained above into a 30 mL Erlenmeyer flask equipped with a stir bar, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-2). (Synthesis Example 5) EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g), and GBL (11.3 g) were measured into a 100 mL round-bottom flask equipped with a stirrer and a nitrogen inlet tube, and dissolved while stirring under nitrogen. CA-2 (1.64 g, 7.50 mmol), NMP (1.23 g), and GBL (1.23 g) were added to this diamine solution while stirring under water cooling, and the mixture was stirred at 70°C for 20 hours under nitrogen. Then, DI-1 (4.19 g, 16.8 mmol), NMP (3.14 g), and GBL (3.14 g) were added, and the mixture was stirred at 23°C for 6 hours under nitrogen to obtain a polymer solution (viscosity: 367 mPa·s). Take 5.0 g of the polymer solution obtained above into a 30 mL Erlenmeyer flask equipped with a stir bar, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-3). (Synthesis Example 6) EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g), and GBL (11.3 g) were measured into a 100 mL flask equipped with a stirrer and a nitrogen inlet tube, and dissolved while stirring under nitrogen. CA-2 (0.82 g, 3.75 mmol), NMP (0.61 g), and GBL (0.61 g) were added to this diamine solution while stirring under water cooling, and the mixture was stirred at 70°C for 20 hours under nitrogen. Then, DI-1 (5.13 g, 20.5 mmol), NMP (3.85 g), and GBL (3.85 g) were added, and the mixture was stirred at 23°C for 6 hours under nitrogen to obtain a polymer solution (viscosity: 1120 mPa·s). Take 5.0 g of the polymer solution obtained above into a 30 mL Erlenmeyer flask equipped with a stir bar, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-4). (Synthesis Example 7) EG-1 (15.0 g, 25.0 mmol), NMP (11.3 g), and GBL (11.3 g) were measured into a 100 mL flask equipped with a stirrer and a nitrogen inlet tube. The mixture was stirred while supplying nitrogen to dissolve the diamine solution. While stirring this diamine solution under water cooling, CA-2 (5.34 g, 24.5 mmol), NMP (4.00 g), and GBL (4.00 g) were added. The mixture was stirred at 70°C for 20 hours under nitrogen to obtain a polymer solution (viscosity: 375 mPa·s). Take 5.0 g of the polymer solution obtained above into a 30 mL Erlenmeyer flask equipped with a stir bar, add NMP (7.5 g) and GBL (7.5 g), and stir at room temperature for 2 hours to obtain a diluted polymer solution (polymer-5). The specifications of the polymer solutions obtained from the above synthesis examples are shown in Table 1. In Table 1, the values ​​in parentheses for the solvent composition represent the amount (parts by mass) of each solvent relative to the total amount of solvent in each solution in 100 parts by mass. [Table 1]

[0121] [Preparation of Liquid Crystal Alignment Agents] (Example 1) In a 50 mL Erlenmeyer flask equipped with a stir bar, 6.00 g of polyacrylic acid solution (PAA-1) obtained in Synthesis Example 1 and 0.48 g of diluted polymer solution (polymer-1) obtained in Synthesis Example 3 were measured. A solution of NMP (1.31 g), GBL (3.91 g), BCS (4.00 g), and 10% by mass of AD-1 (additive solution) (0.30 g) was added and stirred at room temperature for 2 hours to obtain liquid crystal alignment agent (1).

[0122] (Examples 2-10, Comparative Examples 1-2) The types and amounts of polymer solutions and solvents used are changed as shown in Table 2 below. Otherwise, the same procedure as in Example 1 is followed to obtain liquid crystal alignment agents (2) to (12). [Table 2]

[0123] [Fabrication of FFS-driven liquid crystal cells] A liquid crystal cell comprising a liquid crystal display element having a fringe field switching (FFS) mode. First, prepare the substrate for the electrodes. The substrate is a 30mm × 35mm glass substrate with a thickness of 0.7mm. An ITO electrode with a full-surface pattern, constituting the first layer counter electrode, is formed on the substrate. A SiN (silicon nitride) film, formed using CVD (chemical vapor deposition), is then formed on top of the first layer counter electrode. The second SiN film has a thickness of 300nm and acts as an interlayer insulating film. On top of the second SiN film, a comb-shaped pixel electrode, formed by patterning the ITO film, is disposed as the third layer, forming two pixels, the first and second pixels, each approximately 10mm long and 5mm wide. At this point, the first layer counter electrode and the third layer pixel electrode are electrically insulated by the second SiN film. The third layer of pixel electrodes has a central portion with multiple arranged comb-like teeth, with 3μm wide electrode elements that are bent at an inner angle of 160° and spaced 6μm apart. Each pixel is divided into a first zone and a second zone by the line connecting the bent portions of multiple electrode elements. Comparing the first and second regions of each pixel, the electrode elements constituting them are formed in different directions. Specifically, when the direction of the bend connecting the multiple electrode elements is used as a reference, the first region of the pixel is formed with the electrode elements of the pixel electrode at an 80° clockwise angle, while the second region of the pixel is formed with the electrode elements of the pixel electrode at an 80° counterclockwise angle. In other words, in the first and second regions of each pixel, the direction of the rotational movement (in-plane switching) of the liquid crystal within the substrate surface caused by the voltage applied between the pixel electrode and the opposing electrode is formed in opposite directions. The obtained liquid crystal alignment agent was then filtered through a 1.0 μm pore size filter and spin-coated onto the surface of the prepared electrode substrate (first glass substrate) and the surface of the glass substrate with a 4 μm high columnar spacer on the back side where an ITO film has been formed. After drying on a hot plate at 80°C for 5 minutes, it was calcined in a hot air circulating oven at 230°C for 20 minutes to obtain a 100 nm thick polyimide film. This polyimide film was then rubbed with a silk cloth (YA-20R manufactured by Yoshikawa Chemical Co., Ltd.) (roller diameter: 120 mm, roller speed: 500 rpm, moving speed: 30 mm / sec, push-in length: 0.3 mm, rubbing direction: 180° relative to the direction of the bends of the multiple electrode elements connecting the third layer pixel electrode), ultrasonically irradiated in pure water for 1 minute, and washed. Water droplets were removed by blowing air. Then, the substrate was dried at 80°C for 15 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with liquid crystal alignment films were grouped together, and a sealant (Mitsui Chemicals XN-1500T) was printed on the substrates, preserving the liquid crystal injection port. Another substrate was then bonded together with the liquid crystal alignment film surfaces facing each other and the friction direction antiparallel. The substrates were then heat-treated at 150°C for 60 minutes to harden the sealant, creating empty cells with a 4μm intercellular gap. These empty cells were then injected with negative liquid crystal MLC-7026-100 (Merck) using a reduced-pressure injection method, and the injection port was sealed to obtain an FFS-type liquid crystal cell. The obtained liquid crystal cell was then heated at 120°C for 1 hour and placed at 23°C overnight for evaluation. [Evaluation of alignment stability affected by long-term communication] This evaluation assesses the image retention (also known as AC image retention) caused by the deterioration of the alignment performance of the liquid crystal alignment film under long-term AC driving. Using the liquid crystal cell fabricated above, an AC voltage of ±12V at a frequency of 60Hz was applied for 120 hours under a high-brightness backlight (luminance: 20000 cd / m²) with a surface temperature of 50°C. Afterwards, the pixel electrode and the opposing electrode of the liquid crystal cell were short-circuited, and the cell was left at room temperature for one day. Following this, the liquid crystal cell was placed between two polarizing plates configured with their polarization axes orthogonal. The backlight was then turned on without any applied voltage. The arrangement angle of the liquid crystal cell was adjusted to minimize the transmitted light intensity of region 1 of the first pixel. The rotation angle required to minimize the transmitted light intensity of region 2 of the first pixel was calculated and recorded as angle Δθ. The same angle Δθ was calculated for region 2 of the second pixel, comparing it to region 1. The average angle Δθ of the first and second pixels was then calculated as the rotation angle Δθ of the liquid crystal cell. Regarding the stability of liquid crystal alignment, a smaller value of the rotation angle Δθ is considered better. As for the evaluation criteria, a value of Δθ for the liquid crystal cell rotation angle obtained above is rated as "0" if it is below 0.10 degrees, "△" if it is above 0.10 degrees but below 0.20 degrees, and "×" if it is above 0.20 degrees. The results are shown in Table 3. Fabrication of liquid crystal cells for pretilt angle evaluation First, prepare the substrate for attaching the electrodes. The substrate is a glass substrate with a size of 30mm × 40mm and a thickness of 1.1mm. An ITO electrode with a film thickness of 35nm is formed on the substrate. The electrode uses a stripe pattern with a spacing of 40mm vertically and 10mm horizontally. Then, the obtained liquid crystal alignment agent was filtered through a filter with a pore size of 1.0 μm and coated onto the prepared electrode substrate by spin coating. After drying on a hot plate at 80°C for 2 minutes, it was calcined in an infrared furnace at 230°C for 20 minutes to form a 100 nm thick coating, obtaining a substrate with a liquid crystal alignment film. This liquid crystal alignment film was then subjected to friction treatment with a spinning cloth (Yoshikawa Chemical, YA-20R) (roller diameter: 120 mm, roller speed: 1000 rpm, moving speed: 20 mm / sec, push-in length: 0.4 mm), followed by ultrasonic irradiation in pure water for 1 minute for cleaning. After removing water droplets by blowing air, it was dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with attached liquid crystal alignment films were prepared. On one substrate, spherical spacers with a particle size of 4 μm were dispersed on the surface of the liquid crystal alignment film. The liquid crystal injection port was left open, and a sealant (Mitsui Chemicals XN-1500T) was printed around it. The other substrate was then bonded together with the friction direction reversed and the film surfaces facing each other. The substrate was then heated at 150°C for 60 minutes to harden the sealant, creating a void cell. This void cell was then injected with negative liquid crystal MLC-7026 (Merck) using a depressurized injection method. The injection port was then sealed to obtain the liquid crystal cell. The obtained liquid crystal cell was then heated at 120°C for 1 hour and placed at 23°C overnight for various evaluations. [Determination of Pretilt Angle] The pretilt angle within the liquid crystal cells was measured using an AxoScan Mueller matrix polarimeter manufactured by OPTOMETRICS. A lower pretilt angle value is considered better. The results are shown in Table 3.

[0124] [Table 3]

[0125] By using the liquid crystal alignment agent of the embodiments of the present invention, a pretilt angle of less than 1.5 degrees can be obtained. Furthermore, it is generally not easy to obtain good liquid crystal alignment when using negative liquid crystal as liquid crystal material, but by using the liquid crystal alignment agent of the embodiments of the present invention, even when using negative liquid crystal as liquid crystal material, a liquid crystal display element with good liquid crystal alignment (i.e., excellent AC retention characteristics) can still be obtained.

[0126] Furthermore, the entire contents of the specification, scope of the application, drawings and abstract of Japanese Patent Application No. 2021-176518, filed on October 28, 2021, are hereby incorporated and cited as disclosures in the specification of this invention.

Claims

1. A polymer composition characterized by comprising the following (A) and (B) components: (A) a polymer (A), selected from at least one polyimide precursor having a repeating unit represented by formula (a) and polyimides constituting a polyimide derivative of the polyimide precursor; (B) a polyester (B), having a repeating unit represented by formula (b1) and not having the repeating unit represented by formula (a) and its polyimide derivative structure, where X represents a tetravalent organic group, Y represents a divalent organic group derived from a diamine, each of the two Rs independently represents a hydrogen atom or a monovalent organic group, and each of the two Zs independently represents a hydrogen atom or a monovalent organic group. Xar represents a tetravalent organic group derived from an aromatic tetracarboxylic acid dianhydride or its derivatives. The two Rs each independently represent a hydrogen atom or a monovalent organic group. E represents a divalent organic group derived from an organic diol by removing the hydrogen atoms contained in the two hydroxyl groups. The organic diol contains a divalent organic group represented by the following formula (EG). n is an integer greater than or equal to 5. R represents a hydrogen atom or a methyl group.

2. The polymer composition as claimed in claim 1, wherein, In this formula (EG), n is an integer from 5 to 40.

3. The polymer composition as claimed in claim 1 or 2, wherein, The organic diol in formula (b1) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by formula (EG).

4. The polymer composition as claimed in claim 1 or 2, wherein, In formula (b1), Xar is derived from the tetravalent organic group of tetracarboxylic dianhydride or its derivative represented by formula (t). X1 is selected from the structures in formulas (X1-24) and (X1-25), and * represents an atomic bond. In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1. A1 and A2 each independently represent a single bond, -O-, -CO-, -COO-, phenyl, sulfonyl, or amino group. Multiple A2s may be the same or different.

5. The polymer composition as claimed in claim 4, wherein, Equations (X1-24) and (X1-25) are any one of the following equations (X1-26) to (X1-41).

6. The polymer composition as claimed in claim 1 or 2, wherein, The polyester (B) further has repeating units represented by the following formula (b2), where A1 is a divalent organic group derived from diisocyanate, and A2 is a divalent organic group derived from an organic diol by removing the hydrogen atoms contained in the two hydroxyl groups.

7. The polymer composition as claimed in claim 1 or 2, wherein, In formula (a), Y is a divalent organogroup of a diamine selected from the group consisting of diamines represented by formula (O), diamines having amide or urea bonds, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ketone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene, diamines represented by formula (do), 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, and diamines having the group "-N(D)-". D represents a protecting group that will be removed and replaced by a hydrogen atom upon heating. Ar represents a divalent benzene ring, a biphenyl structure, or a naphthalene ring. Two Ars can be the same or different. Any hydrogen atom of the aforementioned benzene ring, biphenyl structure, or naphthalene ring can also be replaced by a monovalent group. p is an integer of 0 or 1. Q2 represents a group that replaces at least a portion of -(CH2)n- or -CH2- of -(CH2)n- with any one of -O-, -C(=O)-, or -OC(=O)-. n is an integer from 2 to 18. When there are more than two m, the two or more m can be the same or different. One or more hydrogen atoms on the benzene ring can also be replaced by a monovalent group.

8. The polymer composition as claimed in claim 6, wherein, In formula (b2), A1 is derived from the divalent organic group of diisocyanate (DIEG), aromatic diisocyanate other than diisocyanate (DIEG), or aliphatic diisocyanate other than diisocyanate (DIEG), which has a divalent organic group represented by formula (EG).

9. The polymer composition as claimed in claim 6, wherein, The organic diol in formula (b2) is a diol containing the divalent organic group represented by formula (EG) above.

10. The polymer composition as claimed in claim 9, wherein, A diol containing a divalent organic group represented by formula (EG) is a diol in which hydrogen atoms are bonded to both ends of the divalent organic group represented by formula (EG).

11. The polymer composition as claimed in claim 1 or 2, wherein, X in (a) is a tetravalent organic group derived from acyclic aliphatic tetracarboxylic dianhydride or its derivatives, a tetravalent organic group derived from alicyclic tetracarboxylic dianhydride or its derivatives, or a tetravalent organic group derived from aromatic tetracarboxylic dianhydride or its derivatives.

12. The polymer composition as claimed in claim 1 or 2, wherein, In formula (a), X is derived from the tetravalent organic group of tetracarboxylic dianhydride or its derivative represented by formula (t). X1 is selected from the structures in formulas (X1-1) to (X1-25), where * represents an atomic bond. In formulas (X1-1) to (X1-4), R1 to R21 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organic group with 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group, where * represents an atomic bond. In formulas (X1-24) to (X1-25), j and k are integers of 0 or 1. A1 and A2 each independently represent a single bond, -O-, -CO-, -COO-, phenyl, sulfonyl, or amide group. Multiple A2s may be the same or different.

13. The polymer composition of claim 1 or 2, wherein the polymer (A) further has repeating units represented by the following formula (U), where U1 is a divalent organic group, U1' is a divalent organic group derived from a diamine, and C1 and C1' are each independently a hydrogen atom or a monovalent organic group.

14. The polymer composition as claimed in claim 1 or 2, wherein, Polymer (A) is a polymer with sealed ends.

15. The polymer composition as claimed in claim 5, wherein, The proportion of repeating units represented by (b1) is 10 mol% or more of all repeating units constituting polyester (B).

16. The polymer composition of claim 1 or 2 further contains at least one additive component selected from the group consisting of crosslinking compounds, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds used to adjust the dielectric constant and / or resistance of the resin film.

17. The polymer composition as claimed in claim 1, wherein, The polyester (B) does not have repeating units represented by the following formula (b2), where A1 is a divalent organic group derived from diisocyanate, and A2 is a divalent organic group derived from an organic diol from which hydrogen atoms contained in two hydroxyl groups have been removed.

18. A liquid crystal alignment agent comprising a polymer composition as claimed in any one of claims 1 to 17.

19. A resin film obtained using a polymer composition as claimed in any one of claims 1 to 17.

20. A liquid crystal alignment film formed using the liquid crystal alignment agent as claimed in claim 18.

21. A liquid crystal display element comprising a liquid crystal alignment film as claimed in claim 20.

22. A method for manufacturing a liquid crystal display element, comprising the following steps (1) to (3): Step (1): applying a liquid crystal alignment agent as claimed in claim 18 onto a substrate; Step (2): calcining the applied liquid crystal alignment agent to obtain a film; Step (3): performing alignment treatment on the film obtained in step (2).

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