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

Abstract

Provided is a polymer composition from which a liquid crystal alignment film, with which a substrate is less likely to peel off, can be obtained, and a liquid crystal display element having high durability against an external pressure can be obtained.　This polymer composition contains a polymer (P) having at least one structural unit selected from the group consisting of formulae (m-1) and (m-2), and an organic solvent. (R1 and R2 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1-3 carbon atoms. R represents a hydrogen atom or an alkyl group having 1-10 carbon atoms. Rs represents a hydrogen atom or an alkyl group having 1-3 carbon atoms. X represents: a group including an oxazoline ring structure; a group including a partial structure "-NRaRb" (where, Ra and Rb each independently represent a hydrogen atom, a C1-C10 monovalent hydrocarbon group, or protective group, and at least one among Ra and Rb represents a protective group); a group including an oxetane ring; a group including a cyclic carbonate group; a group including -SiRm(OR')m' (R and R' each independently represent a hydrogen atom, or an alkyl group having 1-5 carbon atoms, m and m' each represent an integer satisfying m+m'=3, and m' represents an integer of at least 1.); or a group including a benzene ring substituted with a methylol group.)

Description

[Technical Field]

[0001] The present invention relates to a polymer composition, a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a method for producing a liquid crystal display element. [Background technology]

[0002] Liquid crystal display elements are widely used in personal computers, mobile phones, smartphones, televisions, etc. In recent years, there have been increasing opportunities for liquid crystal display elements to be used in high temperature and high humidity environments, such as in car navigation systems and meters installed in vehicles, and in the displays of industrial equipment and measuring instruments installed outdoors.

[0003] This type of liquid crystal display element generally comprises a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, a liquid crystal alignment film that controls the orientation of the liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch the electrical signals supplied to the pixel electrodes.

[0004] In a liquid crystal display element, a liquid crystal layer sandwiched between a pixel electrode and a common electrode functions as a liquid crystal cell. If the voltage holding ratio (VHR) of a liquid crystal cell is low, it becomes difficult to apply sufficient voltage to the liquid crystal molecules even when a voltage is applied. As a result, when used in high temperature and humidity environments or for long periods of time, the display contrast may decrease and flicker may occur, making the display difficult to see. In particular, VA-type LCD elements are used in televisions and in-car displays due to their high contrast and wide viewing angle. These LCD elements use backlights that generate a lot of heat to achieve high brightness, and in in-car applications such as car navigation systems and instrument panels, they are often used or left in high-temperature environments for long periods of time, resulting in a more pronounced decrease in voltage holding ratio.

[0005] In the VA method, in which liquid crystal molecules aligned perpendicular to the substrate are made to respond to an electric field, a technology is known in which a photopolymerizable compound is added to the liquid crystal composition in advance, a vertical alignment film such as a polyimide film is used, and ultraviolet light is irradiated while a voltage is applied to the liquid crystal cell, thereby increasing the response speed of the liquid crystal (PSA (Polymer Sustained Alignment) type element, see, for example, Patent Document 1 and Non-Patent Document 1). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2003-307720 [Patent Document 2] Japanese Patent Publication No. 58-68722 [Non-patent literature]

[0007] [Non-Patent Document 1] K.Hanaoka,SID 04 DIGEST, P1200-1202 Summary of the Invention [Problem to be solved by the invention]

[0008] Touch-panel LCD displays are required to be highly durable against external pressure, such as pressure from a finger or a pointing device such as a pen. This means that they are less likely to develop alignment defects or bright spots even when subjected to external pressure. Furthermore, as tablet and mobile devices become lighter and thinner, the panel assembly process during LCD display manufacturing is more likely to cause panel distortion and internal stress. Such panel distortion and stress can cause the alignment film to peel from the substrate, resulting in bright spots and alignment defects. Therefore, liquid crystal alignment films are required to be less susceptible to substrate peeling. Furthermore, in tablet and mobile devices, to maximize the display surface, the width of the sealant used to bond the substrates of the liquid crystal display element must be narrower than conventional sealants. In such cases, to prevent damage to the liquid crystal display element, the adhesion (also known as adhesion) between the liquid crystal alignment film and the sealant must be stronger than conventional sealants.

[0009] On the other hand, Patent Document 2 describes a polymer having a structural unit containing a maleic anhydride skeleton, but this polymer has a structure different from that of the polymer (P) of the present invention described below. Furthermore, Patent Document 2 does not consider the above-mentioned problem of obtaining a liquid crystal alignment film that is less likely to peel off from the substrate.

[0010] One object of the present invention is to provide a polymer composition that can provide a liquid crystal alignment film that is resistant to substrate peeling and can provide a liquid crystal display element that is highly durable against external pressure. Another object of the present invention is to provide a polymer composition that can provide a liquid crystal alignment film that has high adhesion between the liquid crystal alignment film and a sealant and that increases the strength of the liquid crystal display element. Still another object of the present invention is to provide a polymer composition that can provide a liquid crystal alignment film that has a high voltage holding ratio even when used in a high-temperature environment. [Means for solving the problem]

[0011] The inventors have found that the above object can be achieved by a polymer composition containing a polymer (P) having a specific structural unit and an organic solvent, and have completed the present invention.

[0012] The present invention is based on this finding and has the following gist. A polymer composition comprising a polymer (P) having at least one structural unit selected from the group consisting of the following formulae (m-1) and (m-2), and an organic solvent: [ka] (R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Rs represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a group containing an oxazoline ring structure, a partial structure "-NR a R b ” (However, R a and R b each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a protecting group; R a and R b At least one of the groups represents a protecting group. m (OR') m’ (R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m and m' represent integers that satisfy m+m'=3, and m' represents an integer of 1 or greater), or a group that contains a benzene ring substituted with a methylol group.) [Effects of the Invention]

[0013] According to the present invention, a polymer composition is provided that can obtain a liquid crystal alignment film that is resistant to substrate peeling and can provide a liquid crystal display element that is highly durable against external pressure. Also provided is a polymer composition that can obtain a liquid crystal alignment film that has high adhesion between the liquid crystal alignment film and a sealant and increases the strength of the liquid crystal display element. Furthermore, a polymer composition is provided that can obtain a liquid crystal alignment film that has a high voltage holding ratio even when used in a high-temperature environment. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Polymer composition> The polymer composition of the present invention contains the polymer (P) and an organic solvent. The polymer composition of the present invention can be prepared, for example, by dispersing or dissolving the polymer (P) and, if necessary, other components in an organic solvent.

[0015] <Polymer (P)> The polymer (P) of the present invention has at least one structural unit selected from the group consisting of the following formulae (m-1) and (m-2): That is, the polymer (P) is a maleimide polymer. [ka] (R 1 and R 2 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Rs represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. X represents a group containing an oxazoline ring structure, a partial structure "-NR a R b ” (However, R a and R b each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a protecting group; R a and R b At least one of the groups represents a protecting group. m (OR') m’(R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m and m' represent integers that satisfy m+m'=3, and m' represents an integer of 1 or greater), or a group that contains a benzene ring substituted with a methylol group.)

[0016] In the above formulas (m-1) and (m-2), R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 1 is a hydrogen atom and R 2 is more preferably a hydrogen atom or a methyl group, and R 1 and R 2 It is more preferred that is a hydrogen atom. R is preferably a hydrogen atom. Rs is preferably a hydrogen atom.

[0017] X preferably represents a structure selected from the following formulae (mx-1) to (mx-6), and more preferably represents a structure selected from the following formulae (mx-1) to (mx-2). [ka] (R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. D represents a protecting group. Q1 and Q4 each independently represent an alkylene group or an aryl group having 1 to 20 carbon atoms, Q2 represents a single bond or an alkylene group having 1 to 20 carbon atoms. Q3 and Q6 each represent a single bond, and Q5 represents an alkylene group having 1 to 20 carbon atoms. R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. m and m' represent integers that satisfy the relationship m+m'=3, and m' represents an integer of 1 or greater. In R1 and R2, the hydrogen atom bonded to the alkyl group having 1 to 3 carbon atoms may each independently be substituted with a hydroxy group, —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. * represents a bond.)

[0018] In the above formulas (m-1) and (m-2), the term "protecting group" refers to a group that is eliminated by heating and replaced with a hydrogen atom. Examples of such protecting groups include carbamate-based protecting groups, amide-based protecting groups, imide-based protecting groups, and sulfonamide-based protecting groups. Of these, carbamate-based protecting groups are preferred, and specific examples include tert-butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, 1,1-dimethyl-2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, and 2-(trimethylsilyl)ethoxycarbonyl. Of these, the tert-butoxycarbonyl group is preferred because of its high thermal elimination property and its ability to reduce the amount of deprotected moieties remaining in the film.

[0019] Preferred specific examples of the group represented by the above formula (mx-1) include the following formula (1x-1). [ka] (* represents a bond.) A specific example of the group represented by the above formula (mx-2) is an organic group obtained by removing -NH2 from Boc-hydrazine (tert-butoxycarbonylhydrazine). Specific examples of the group represented by the above formula (mx-5) include organic groups obtained by removing -NH2 from compounds such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltriethoxysilane.

[0020] The polymer (P) of the present invention may contain one or more types of structural units represented by formula (m-1) and (m-2). The total content of the structural units represented by formula (m-1) and (m-2) is preferably 5 to 80 mol %, more preferably 10 to 50 mol %, based on the total structural units of the polymer (P).

[0021] A polymer having a structural unit represented by the above formula (m-1) can be obtained, for example, by reacting a polymer having a structural unit containing a maleic anhydride skeleton (maleic anhydride polymer) with one or more primary or secondary amine compounds. In this reaction, an amino group of the primary or secondary amine compound is added to the carbonyl group of the maleic anhydride skeleton, and a ring-opening reaction proceeds to obtain the structural unit represented by formula (m-1).

[0022] The polymer having a structural unit containing a maleic anhydride skeleton is preferably a maleic anhydride polymer containing a structural unit represented by the following formula (m) (hereinafter also referred to as structural unit (m)), and more preferably a maleic anhydride copolymer (hereinafter also referred to as copolymer (Mp)) containing the structural unit (m) and a structural unit represented by the following formula (v) (hereinafter also referred to as structural unit (v)): [ka] (R 1 and R 2 R each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. 3 , R 4 , R 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -OC(=O)-R (R represents an alkyl group having 1 to 6 carbon atoms), -C(=O)-OR (R represents an alkyl group having 1 to 6 carbon atoms), -OR (R represents an alkyl group having 1 to 6 carbon atoms), or a phenyl group.

[0023] Examples of the structural unit (v) include ethylene, propylene, n-butene, isobutylene, n-pentene, n-hexene, alkyl acrylates and methacrylates having 1 to 4 carbon atoms, vinyl acetate, methyl vinyl ether, and [ka] (R is hydrogen or an alkyl group having 1 to 6 carbon atoms, and the benzene ring may be optionally substituted with an alkyl group having 1 to 4 carbon atoms or a hydroxy group.)

[0024] Preferred examples of alkyl acrylates having 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, and mixtures thereof. Preferred examples of alkyl methacrylates having 1 to 4 carbon atoms include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, and mixtures thereof. A mixture of alkyl methacrylates having 1 to 4 carbon atoms and alkyl acrylates having 1 to 4 carbon atoms may also be used. Preferred examples of styrenic compounds include styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and mixtures thereof. As the monomer component for obtaining the maleic anhydride copolymer, a mixture of a styrenic compound, ethylene, propylene, n-butene, isobutylene, n-pentene, n-hexene, alkyl acrylates and / or methacrylates having 1 to 4 carbon atoms may be used. Among ethylene, propylene, n-butene, isobutylene, n-pentene, and n-hexene, isobutylene or a mixture of isobutylene, 1-butene, and 2-butene is particularly preferred.

[0025] The structural unit (m) preferably accounts for 10 to 50 mol %, and particularly preferably 30 to 50 mol %, of all structural units constituting the copolymer (Mp).

[0026] The molecular weight of the copolymer (Mp) is preferably a weight average molecular weight of 3,000 to 500,000, more preferably 8,000 to 150,000.

[0027] The method for obtaining the polymer having a structural unit containing the maleic anhydride skeleton is not particularly limited, but for example, it can be obtained by polymerizing a compound (monomer) that forms a structural unit represented by the structural unit (m), and optionally a compound (monomer) that forms a structural unit represented by (v), and compounds (monomers) that form other structural units. Alternatively, a commercially available product such as ISOBAM in the examples described below may be used.

[0028] Examples of the primary or secondary amine compound include specific amine compounds (A) represented by "HN(Rs)(X)." Here, Rs and X are defined as in the formula (m-1). Specific examples of the specific amine compound (A) include compounds represented by the following formulas (a-1) to (a-6). [ka] (In the formula, R1, R2, D, Q1, Q2, Q3, Q4, Q5, Q6, R, R', m, and m' are defined as in the above formulas (mx-1) to (mx-6). Rs is defined as in the above formula (m-1).)

[0029] The reaction between the polymer having a structural unit containing a maleic anhydride skeleton and a primary or secondary amine compound is preferably carried out in an organic solvent. Examples of the organic solvent that can be used include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. In the reaction, the reaction temperature is preferably 30 to 120°C, and the reaction time is preferably 1 to 24 hours. The reaction solution in which the polymer is dissolved may be used as it is, or the polymer contained in the reaction solution may be isolated using a known isolation method, such as a method of pouring the reaction solution into a large amount of poor solvent and drying the resulting precipitate under reduced pressure, or a method of distilling the reaction solution under reduced pressure using an evaporator, and then the polymer may be used for preparing a polymer composition.

[0030] The reaction amount of the primary or secondary amine compound is preferably 0.01 to 1.2 equivalents, more preferably 0.1 to 1.2 equivalents, and even more preferably 0.1 to 1.0 equivalents, relative to the anhydride group possessed by the structural unit (m).

[0031] A polymer having a structural unit represented by the above formula (m-1), in which R is an alkyl group having 1 to 10 carbon atoms, can be obtained, for example, by esterifying a polymer having a structural unit represented by the above formula (m-1), in which R is hydrogen. The esterification can be carried out in the same manner as in the method for obtaining a polyamic acid ester from a polyamic acid, which will be described later.

[0032] A polymer having a structural unit represented by the formula (m-2) can be obtained by ring-closing a polymer having a structural unit represented by the formula (m-1). The polymer (P) of the present invention may contain a structural unit represented by the formula (m-1) in addition to the structural unit represented by the formula (m-2). Methods for obtaining a polymer having a structural unit represented by the formula (m-2) include thermal imidization, in which a solution of a polymer having a structural unit represented by the formula (m-1) is heated as is, and catalytic imidization, in which a catalyst is added. When thermal imidization is performed in a solution, the temperature is 100 to 400°C, preferably 120 to 250°C, and it is preferable to perform the imidization while removing water generated by the imidization reaction from the system.

[0033] The catalytic imidization can be carried out by adding a basic catalyst, and if necessary, an acid anhydride, to a polymer solution having a structural unit represented by formula (m-1), and stirring the mixture at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the molar amount of the amic acid groups, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the molar amount of the amic acid groups. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and N,N-dimethyl-4-aminopyridine.

[0034] In the present invention, by using a polymer composition containing the polymer (P) having the above-mentioned specific structural unit and an organic solvent, it is possible to obtain a liquid crystal alignment film that is resistant to substrate peeling and a liquid crystal display device that is highly durable against external pressure, as specifically illustrated in the examples described below. Although the mechanism behind this is not entirely clear, the following is thought to be one of the reasons. It is believed that the thermal condensation of polar groups such as carboxyl groups contained in polymer (P) or hydroxyl groups or carboxyl groups contained in other polymers or substrates with the moiety contained in formula (m-1) generates chemical bonds within the molecules of polymer (P) and between them and other polymers or substrates. It is believed that crosslinking of polymer (P), which has a flexible structure, improves the hardness and toughness of the film itself, and that the uncrosslinked carboxyl groups also improve adhesion to the substrate.

[0035] The polymer (P) of the present invention may have structural units represented by formulae (m) and (v) in addition to the structural units represented by formulae (m-1) and (m-2). The polymer (P) of the present invention may further have structural units other than the structural units represented by formulae (m), (m-1), (m-2) and (v). Examples of structural units other than the structural units represented by formulae (m), (m-1), (m-2) and (v) include structural units represented by the following formulae (m-3) to (m-4) or structural units derived from other compounds having an ethylenic double bond. [ka] (R 1 , R 2 , R, and Rs are defined as in the above formulae (m-1) to (m-2). Y represents a hydrogen atom or a monovalent organic group other than X in the above formulae (m-1) to (m-2).

[0036] Specific examples of the monovalent organic group for Y in formulas (m-3) and (m-4) include carboxyl group-containing monoamines such as p-aminobenzoic acid; alicyclic group-containing monoamines such as cyclohexylamine; alkyl group-containing monoamines such as n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-eicosylamine; or monovalent organic groups derived from aniline.

[0037] Examples of the other compounds having an ethylenic double bond include carboxyl group-containing compounds such as acrylic acid, methacrylic acid, α-ethylacrylic acid, 2-hydroxyethyl(meth)acrylic acid, 4-vinylbenzoic acid, and maleic acid; hydroxy group-containing compounds such as 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, and N-methylol(meth)acrylamide; isooctyl acrylate, isodecyl acrylate, and lauryl acrylate, decyl methacrylate, stearyl acrylate, and other long-chain alkyl group-containing compounds; alicyclic group-containing compounds such as cyclohexyl (meth)acrylate; benzene ring-containing compounds such as 2-phenoxyethyl acrylate and ethoxylated nonylphenyl acrylate; oxiranyl group-containing compounds such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and 4-(glycidyloxy)butyl (meth)acrylate; compounds having an isocyanate group or a protected isocyanate group such as 2-methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko K.K.) and 2-[(3,5-dimethylpyrazoyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP, manufactured by Showa Denko K.K.); and compounds having a tetrahydropyranyl group such as tetrahydrofurfuryl methacrylate.

[0038] The polymer (P) of the present invention may contain one type of structural unit represented by formula (m) alone or two or more types thereof. The content of the structural unit represented by formula (m) is preferably 5 to 90 mol %, more preferably 10 to 50 mol %, based on the total structural units of the polymer (P). The polymer (P) of the present invention may contain one type of structural unit represented by formula (v) alone or two or more types thereof. The content of the structural unit represented by formula (v) is preferably 50 to 90 mol %, more preferably 30 to 70 mol %, based on the total structural units of the polymer (P). However, the total content of the structural unit represented by formula (m), the structural unit represented by formula (m-1) and the structural unit represented by formula (m-2) in polymer (P) of the present invention is the same as the content of the structural unit represented by formula (m) contained in the maleic anhydride polymer used to obtain polymer (P) of the present invention.

[0039] The content of the polymer (P) used in the present invention is preferably 1 to 100 mass %, more preferably 5 to 70 mass %, and even more preferably 10 to 50 mass %, based on the total amount of polymer components contained in the polymer composition. The polymer (P) can be used alone or in combination of two or more. The total content of the polymer components contained in the polymer composition of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution.

[0040] <Polymer (Q)> The polymer composition of the present invention may further contain polymer (Q), which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid-polyamic acid ester copolymer, polyimide, polyamide, polyorganosiloxane, poly(meth)acrylate, and polyester. Polymer (Q) is preferably contained in order to improve the solution properties of the liquid crystal alignment agent and the electrical properties of the liquid crystal alignment film. The polyimide is obtained by imidizing the polyamic acid, polyamic acid ester, or polyamic acid-polyamic acid ester copolymer. The polyamic acid, polyamic acid ester, or polyamic acid-polyamic acid ester copolymer is preferably obtained by polymerizing a diamine component and a tetracarboxylic acid component.

[0041] <Diamine component> Examples of the diamine component include diamines having a carboxyl group such as p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, and 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, and 1,4-bis(4-aminophenoxy) )benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethyl)ether (oxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 1, Diamines having a urea bond such as 3-bis(4-aminophenethyl)urea, diamines having a terminal photopolymerizable group such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline, diamines having a radical initiation function such as those represented by the following formulae (R1) to (R5), diamines having a photosensitizing function that shows a sensitizing effect upon irradiation with light such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 9,9-bis(4-aminophenyl)fluorene, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,Examples of suitable diamines include 4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, diamines having a heterocycle such as those represented by the following formulae (z-1) to (z-18), diamines having a diphenylamine skeleton such as those represented by the following formulae (Dp-1) to (Dp-3), diamines having the group "-N(D)-" (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom, preferably a tert-butoxycarbonyl group) such as those represented by the following formulae (5-1) to (5-11), diamines having an oxazoline structure such as those represented by the following formulae (Ox-1) to (Ox-2), diamines having a structure in the side chain that exhibits vertical alignment of liquid crystal such as those represented by the following formulae (V2-1) to (V2-13), and organosiloxane-containing diamines such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane. The diamines may be used alone or in combination of two or more.

[0042] [ka] [ka] [ka] (In formulas (R3) to (R5), n is an integer of 2 to 6.)

[0043] [ka] [ka] (Boc represents a tert-butoxycarbonyl group.)

[0044] [ka] [ka]

[0045] [ka] (X v1 ~X v4 , X p1 ~X p8 are each independently -(CH2) a - (a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CHO-, -CH2-OCO-, -COO-, or -OCO-; X v5 represents -O-, -CHO-, -CHO-, -COO-, or -OCO-; X V6 ~X V7 , X s1 ~X s4 are each independently -O-, -(CH2) n X represents -O- (n is an integer of 1 to 6), -COO- or -OCO-. a ~X f is a single bond, -O-, -NH-, or -O-(CH2) m -O- (m is an integer of 1 to 8), R v1 ~R v4 , R 1a ~R 1h are each independently, -C n H 2n+1 (n is an integer from 1 to 20), or -OC n H 2n+1 (n is an integer from 2 to 20).

[0046] Further, examples of the diamine component include aliphatic diamines such as metaxylenediamine, alicyclic diamines such as 4,4-methylenebis(cyclohexylamine), and diamines described in WO 2016 / 125870.

[0047] <Tetracarboxylic acid component> The tetracarboxylic acid component refers to a component containing at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives, such as tetracarboxylic acid dihalides, tetracarboxylic acid dianhydrides, tetracarboxylic acid diester dichlorides, and tetracarboxylic acid diesters. Examples of the tetracarboxylic acid component include aromatic tetracarboxylic acid dianhydrides, acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and derivatives thereof. The aromatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The acyclic aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not need to be composed solely of a chain hydrocarbon structure, and it may partially contain an alicyclic structure or an aromatic ring structure. The alicyclic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, it does not need to be composed solely of an alicyclic structure, and it may partially contain a chain hydrocarbon structure or an aromatic ring structure. The tetracarboxylic dianhydrides or derivatives thereof may be used singly or in combination of two or more kinds.

[0048] The tetracarboxylic acid component preferably contains a tetracarboxylic dianhydride represented by the following formula (3) or a derivative thereof. [ka] X represents a structure selected from the following (x-1) to (x-13). [ka] (R 1 ~R 4R each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a phenyl group. 5 and R 6 each independently represents a hydrogen atom or a methyl group. j and k each independently represent 0 or 1. A1 and A2 each independently represent a single bond, -O-, -CO-, -COO-, phenylene, a sulfonyl group, or an amide group. *1 represents a bond bonded to one acid anhydride group, and *2 represents a bond bonded to the other acid anhydride group. Two A2s may be the same or different.

[0049] Preferred specific examples of the above (x-12) and (x-13) include the following formulae (x-14) to (x-29), in which "*" represents a bond. [ka] [ka]

[0050] Preferred examples of the tetracarboxylic dianhydride represented by the above formula (3) or a derivative thereof include tetracarboxylic dianhydrides represented by the formula (3) or a derivative thereof in which X is represented by the above formulae (x-1) to (x-7) and (x-11) to (x-13).

[0051] <Production of polyimide precursor (polyamic acid)> Examples of the polyimide precursor used in the present invention include polyamic acid, polyamic acid ester, polyamic acid-polyamic acid ester copolymer, etc. In this specification, polyimide precursors or polyimides are also collectively referred to as polyimide-based polymers. The polyamic acid, which is the polyimide precursor used in the present invention, can be produced, for example, by the following method: Specifically, the polyamic acid can be synthesized by reacting a diamine component with a tetracarboxylic acid component in the presence of an organic solvent at −20 to 150° C., preferably 0 to 80° C., for 30 minutes to 24 hours, preferably 1 to 12 hours.

[0052] The reaction between the diamine component and the tetracarboxylic acid component is usually carried out in an organic solvent. The organic solvent used is not particularly limited as long as it dissolves the produced polyimide precursor. Specific examples of organic solvents used in the reaction include, but are not limited to, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. In addition, when the polyimide precursor has high solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or an organic solvent represented by the following formulas [D-1] to [D-3] can be used. [ka] In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, and 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. These organic solvents may be used alone or in combination. Furthermore, even if a solvent does not dissolve the polyimide precursor, it may be mixed with the above-mentioned solvent to the extent that the resulting polyimide precursor does not precipitate.

[0053] The concentration of the polyamic acid polymer in the reaction system is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoints that precipitation of the polymer is unlikely to occur and a high molecular weight polymer is easily obtained.

[0054] The polyamic acid obtained as described above can be recovered by pouring the reaction solution into a poor solvent while stirring it thoroughly to precipitate the polymer. Alternatively, the precipitation can be repeated several times, followed by washing with a poor solvent and drying at room temperature or by heating to obtain a purified polyamic acid powder. The poor solvent is not particularly limited, but examples include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

[0055] <Production of Polyimide Precursors (Polyamic Acid Esters, Polyamic Acid-Polyamic Acid Ester Copolymers)> The polyamic acid ester and polyamic acid-polyamic acid ester copolymer, which are polyimide precursors used in the present invention, can be produced, for example, by (1) an esterification reaction of polyamic acid using an esterifying agent, (2) a reaction of a tetracarboxylic acid diester dichloride with a diamine, or (3) a polycondensation reaction of a tetracarboxylic acid diester with a diamine.

[0056] Among the above three production methods, the above production method (1) or (2) is particularly preferred because it allows the production of high molecular weight polyamic acid esters and polyamic acid-polyamic acid ester copolymers. The polyamic acid ester or polyamic acid-polyamic acid ester copolymer solution obtained as described above can be poured into a poor solvent while being thoroughly stirred to precipitate the polymer. Precipitation is carried out several times, followed by washing with a poor solvent and drying at room temperature or by heating, to obtain a purified powder of polyamic acid ester or polyamic acid-polyamic acid ester copolymer. The poor solvent is not particularly limited, but examples include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

[0057] <Production of Polyimide> The polyimide used in the present invention can be produced by imidizing the above-mentioned polyimide precursor.

[0058] Imidization can be carried out by stirring the polyamic acid to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. The organic solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among these, pyridine is preferred because it has a suitable basicity for promoting the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after the reaction.

[0059] The temperature when carrying out the above imidization reaction is -20 to 140°C, preferably 0 to 100°C, and the reaction time is 0.5 to 100 hours, preferably 1 to 80 hours. The amount of the basic catalyst is 0.5 to 30 times by mole, preferably 2 to 20 times by mole, the amount of the amic acid, and the amount of the acid anhydride is 1 to 50 times by mole, preferably 3 to 30 times by mole, the amount of the amic acid. The imidization rate of the obtained polymer can be controlled by adjusting the amount of the catalyst, temperature, and reaction time. The imidization rate does not necessarily have to be 100% and can be adjusted as desired depending on the application and purpose.

[0060] Since the added catalyst and the like remain in the solution after the imidization reaction of the polyimide precursor, it is preferable to recover the obtained imidized polymer by the means described below, redissolve it in an organic solvent, and use it as a component of the polymer composition of the present invention. The polyimide solution obtained as described above can be poured into a poor solvent while being thoroughly stirred to precipitate the polymer. The precipitation is repeated several times, and the resulting solution is washed with a poor solvent and then dried at room temperature or by heating to obtain a purified polyimide powder. The poor solvent is not particularly limited, but examples thereof include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, and benzene.

[0061] The content of the polymer (Q) used in the present invention is preferably 30 to 95 mass %, more preferably 50 to 90 mass %, based on the total amount of polymer components contained in the polymer composition. The polymer (Q) may be used alone or in combination of two or more.

[0062] <Organic solvents> Examples of the organic solvent contained in the polymer composition of the present invention include lactone solvents such as γ-valerolactone and γ-butyrolactone; lactam solvents such as γ-butyrolactam, N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; 4-hydroxy-4-methyl-2-pentanone, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl Examples of suitable solvents include ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisopentyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1,2-ethanediol, and diisobutylcarbinol (2,6-dimethyl-4-heptanol). These can be used alone or in combination of two or more.

[0063] Preferred solvent combinations include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, and N-methyl-2-pyrrolidone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone. and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, and 4-hydroxy-4-methyl-2-pentanone, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol methyl ether, N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone, N-methyl-2 Examples of suitable solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether, and N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether. The type and content of such solvents are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0064] The content of the organic solvent used in the present invention is preferably from 90 to 99 mass %, more preferably from 91 to 99 mass %, and even more preferably from 92 to 99 mass %, based on the total mass of the polymer composition.

[0065] <Liquid crystal alignment agent> The liquid crystal aligning agent of the present invention contains the polymer composition of the present invention. The liquid crystal aligning agent of the present invention is preferably prepared as a coating liquid so as to be suitable for forming a liquid crystal alignment film. The liquid crystal aligning agent of the present invention can be prepared, for example, by dispersing or dissolving the polymer composition of the present invention and, if necessary, other components in an organic solvent. Examples of the organic solvent include the same organic solvents as those contained in the polymer composition described above. Examples of other components include a crosslinkable compound, a functional silane compound, a surfactant, a compound having a photopolymerizable group, etc.

[0066] The crosslinkable compound can be used for the purpose of increasing the strength of the liquid crystal alignment film. Examples of such crosslinkable compounds include compounds having an epoxy group, an isocyanate group, an oxetane group, or a cyclocarbonate group, or compounds having at least one group selected from the group consisting of a hydroxy group, a hydroxyalkyl group, and a lower alkoxyalkyl group, as described in paragraphs

[0109] to

[0113] of International Publication WO2016 / 047771, as well as compounds having a blocked isocyanate group.

[0067] Blocked isocyanate compounds are commercially available, and examples that can be preferably used include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.).

[0068] Specific examples of preferred crosslinkable compounds include compounds represented by the following formulas (CL-1) to (CL-11). [ka]

[0069] The above are examples of the crosslinkable compound, and the present invention is not limited to these. The crosslinkable compound used in the liquid crystal aligning agent of the present invention may be one type or a combination of two or more types.

[0070] The content of the other crosslinkable compounds in the liquid crystal aligning agent of the present invention 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.

[0071] The functional silane compound can be used to improve the adhesion between the liquid crystal alignment film and the base substrate. Specific examples include the silane compounds described in paragraph

[0019] of International Publication No. 2014 / 119682. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of all polymer components.

[0072] The surfactant can be used to improve the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film. Examples of the surfactant include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples of these surfactants include those described in paragraph

[0117] of International Publication WO2016 / 047771. The amount of the surfactant used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all polymer components contained in the liquid crystal alignment agent.

[0073] Examples of compounds having a photopolymerizable group include compounds having one or more polymerizable unsaturated groups, such as an acrylate group or a methacrylate group, in the molecule, such as compounds represented by the following formulas (M-1) to (M-7).

[0074] [ka]

[0075] Furthermore, the liquid crystal aligning agent of the present invention can contain a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge dissipation in the device. The nitrogen-containing heterocyclic amine compounds represented by formulas [M1] to [M156], more preferably 3-picolylamine and 4-picolylamine, are described in paragraphs

[0194] to

[0200] of International Publication WO 2011 / 132751 (published October 27, 2011). These amine compounds may be added directly to the liquid crystal aligning agent, but are preferably added after being prepared into a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent used is not particularly limited, as long as it dissolves the specific polymer (P).

[0076] When the liquid crystal aligning agent of the present invention contains polyamic acid or polyamic acid ester, an imidization accelerator or the like may be added for the purpose of efficiently promoting imidization by heating when baking the coating film.

[0077] The solid content concentration in the liquid crystal aligning agent or polymer composition of the present invention (the ratio of the total mass of components other than the organic solvent in the liquid crystal aligning agent or polymer composition to the total mass of the liquid crystal aligning agent or polymer composition) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 1 to 10 mass%, more preferably 1 to 9 mass%, and even more preferably 1 to 8 mass%. The particularly preferred range of solid content varies depending on the method used to apply the liquid crystal alignment agent or polymer composition to the substrate. For example, when using a spin coating method, a particularly preferred solid content range is 1.5 to 4.5 mass%. When using a printing method, a particularly preferred solid content range is 3 to 9 mass%, thereby resulting in a solution viscosity range of 12 to 50 mPa·s. When using an inkjet method, a particularly preferred solid content range is 1 to 5 mass%, thereby resulting in a solution viscosity range of 3 to 15 mPa·s.

[0078] <Liquid crystal alignment film / LCD element> The liquid crystal alignment film of the present invention is obtained from the above liquid crystal aligning agent or polymer composition. The liquid crystal alignment film of the present invention can be used for horizontal alignment type or vertical alignment type liquid crystal alignment film, and is particularly suitable for vertical alignment type liquid crystal display elements such as VA mode or PSA mode. The liquid crystal display element of the present invention is equipped with the above liquid crystal alignment film. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (3) or steps (1) to (4).

[0079] (1) Step of applying a liquid crystal alignment agent or a polymer composition onto a substrate The liquid crystal aligning agent or polymer composition of the present invention is applied to one surface of a substrate having a patterned transparent conductive film by an appropriate application method such as a roll coater method, a spin coat method, a printing method, or an inkjet method. The substrate is not particularly limited as long as it is highly transparent, and plastic substrates such as acrylic substrates and polycarbonate substrates can be used in addition to glass substrates and silicon nitride substrates. In addition, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for only one substrate, and in this case, a light-reflecting material such as aluminum can be used for the electrode.

[0080] (2) Baking the coating After applying the liquid crystal aligning agent or polymer composition, it is preferable to first perform preheating (pre-baking) for the purpose of preventing dripping of the applied aligning agent. The pre-baking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C, and the pre-baking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. After the solvent is completely removed, it is preferable to perform a further heating (post-baking) step. The post-baking temperature is preferably 80 to 300° C., more preferably 120 to 250° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0081] The coating film formed in the above step (1) can be used as a liquid crystal alignment film as it is, but the coating film may also be subjected to an alignment ability imparting treatment, such as a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, or cotton, or a photoalignment treatment in which the coating film is irradiated with polarized or unpolarized radiation. In the photo-alignment treatment, the radiation to be irradiated onto the coating film can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, the radiation may be irradiated from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized radiation, the irradiation direction is an oblique direction.

[0082] (3) Forming the liquid crystal layer (3-1) VA type LCD element Two substrates on which liquid crystal alignment films are formed are prepared as described above, and liquid crystal is placed between the two substrates arranged opposite each other. Specifically, the following two methods can be used. The first method is a conventionally known method. First, the two substrates are arranged opposite each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant to contact the film surface, and then the injection hole is sealed. The second method is called the ODF (One Drop Fill) method. A UV-curable sealant, for example, is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant. In either method, it is desirable to further heat the substrate to a temperature at which the liquid crystal composition is in an isotropic phase, and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling.

[0083] (3-2) Manufacturing PSA type liquid crystal display elements The procedure is the same as in (3-1) above, except that a liquid crystal composition containing a polymerizable compound is injected or dropped in. Examples of the polymerizable compound include polymerizable compounds represented by the above formulas (M-1) to (M-7). (3-3) When a coating film is formed on a substrate using a liquid crystal alignment agent or a polymer composition containing a compound having a polymerizable group A method for producing a liquid crystal display element may be employed in which a process similar to that described in (3-1) above is followed by a step of irradiating with ultraviolet light, which will be described later. This method, similar to the production of the PSA-type liquid crystal display element, allows for the production of a liquid crystal display element with excellent response speed with a small amount of light irradiation. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups, such as acrylate or methacrylate groups, in the molecule, as represented by the above formulae (M-1) to (M-7). The content of the compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of all polymer components. The polymerizable group may also be contained in the polymer used in the polymer composition. Examples of such polymers include polymers obtained by reacting a diamine component containing a diamine having the above photopolymerizable group at its terminal.

[0084] (4) UV irradiation process The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above. The voltage applied here can be, for example, 5 to 50 V DC or AC. The light to be irradiated can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiation light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. The light irradiation dose is preferably 1,000 to 200,000 J / m 2 and more preferably 1,000 to 100,000 J / m 2 is.

[0085] A liquid crystal display element can be obtained by laminating a polarizing plate to the outer surface of the liquid crystal cell. Examples of polarizing plates that can be laminated to the outer surface of the liquid crystal cell include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0086] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays. [Example]

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The meanings of the abbreviations for the compounds used in the examples are as follows. <Polymer> ISOBAM: Poly(isobutylene-o-maleic anhydride) Mn: 160,000-170,000 (Kuraray Co., Ltd., ISOBAM-10) <Monomer> (diamine) DBA: 3,5-diaminobenzoic acid 3AMPDA: 3,5-diamino-N-(pyridin-3-ylmethyl)benzamide

[0088] [ka]

[0089] (Tetracarboxylic acid component) PMDA: Pyromellitic anhydride D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride D3: 2,3,5-tricarboxycyclopentylacetic dianhydride (monoamine) (modifier) Boc Hydrazine: Tert-Butyl Carbazate [ka]

[0090] (solvent) NMP: N-methyl-2-pyrrolidone BCS: Ethylene glycol monobutyl ether (catalyst) DMAP: N,N-dimethyl-4-aminopyridine

[0091] <Measurement of molecular weight of polyimide> The molecular weight of the polyimide in the synthesis examples was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Corporation. Column temperature: 50℃ Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) is 30 mmol / L, phosphoric acid anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L) Flow rate: 1.0 ml / min Standard samples for calibration curve preparation: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weights of approximately 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratories (molecular weights of approximately 12,000, 4,000, 1,000).

[0092] <Measurement of imidization rate> The imidization rate of the polymer in the synthesis example was measured as follows. 20 mg of the sample powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku), 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve it. This solution was measured for proton NMR at 400 MHz using an NMR measuring instrument manufactured by Varian (Varian NMR System 400 NB). The imidization rate was determined using the proton peak integration value of the proton derived from the structure that does not change before and after imidization as the reference proton, and the proton peak integration value of the NH group of the amic acid that appears around 9.5 - 10.0 ppm, and was obtained by the following calculation formula. Imidization rate (%) = (1 - α·x / y)×100 (x is the proton peak integration value of the NH group of the amic acid, y is the proton peak integration value of the reference proton, and α is the ratio of the number of reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate of 0%).)

[0093] <Monomer synthesis example 1> Synthesis of MA-1

Chemical formula

[0094] <Synthesis of MA-1-1> Into a four-necked eggplant flask, methanol (320 g), p-nitrobenzonitrile (40.0 g, 270 mmol), 2-amino-2-methyl-propane-1,3-diol (142.3 g, 1.35 mol) and sodium carbonate (28.6 g, 270 mmol) were charged, and the reaction was carried out for 22 hours under reflux conditions in a nitrogen atmosphere. After the reaction was completed, the reaction solution was poured into pure water (960 g) to precipitate crystals, which were filtered and washed with methanol. Subsequently, the obtained crude product was washed by slurry with a mixed solvent of ethyl acetate (260 g) and hexane (40 g), filtered and dried to obtain MA-1-1 as white crystals (yield: 46.8 g, 199 mmol, yield: 74%). 1 H-NMR(400MHz) in DMSO-d6: 8.29-8.33ppm(m,2H), 8.07-8.11ppm(m,2H) 4.97ppm(t,1H), 4.46ppm(d,1H), 4.07ppm(d,1H), 3.36-3.47ppm(m,2H), 1.25ppm(s,3H)

[0095] <Synthesis of MA-1> Into a four-necked eggplant flask, N,N-dimethylformamide (224.5 g), MA-1-1 (28.1 g, 119 mmol) and 5% palladium-carbon (about 50% water-wetted product) (2.44 g) were charged, and the reaction was carried out for about 2 days under room temperature conditions in a hydrogen atmosphere. After the reaction was completed, 5% palladium-carbon was removed by filtration, and N,N-dimethylformamide was removed by concentration under reduced pressure. Subsequently, tetrahydrofuran (60.0 g) was added and stirred overnight at room temperature. After stirring, it was filtered, washed with tetrahydrofuran, and dried to obtain MA-1 as light purple crystals (yield: 19.1 g, 92.6 mmol, yield: 78%). 1 H-NMR(400MHz) in DMSO-d6:7.48-7.51ppm(m,2H),6.51-6.55ppm(m,2H),5.66ppm(s,2H),4.82ppm(t,1H),4.26ppm(d,1H), 3.85ppm(d,1H),3.34ppm(d,2H),1.17ppm(s,3H)

[0096] <Synthesis of maleimide polymers and maleic anhydride polymers> <Synthesis Example 1> Boc hydrazine (1.20 g, 9.1 mmol) was added to NMP (42.3 g) and stirred at 25°C for 10 minutes. Once dissolution was confirmed, DMAP (0.139 g, 1.14 mmol) was added as a reaction catalyst and stirred for an additional 30 minutes. ISOBAM (3.50 g, 22.7 mmol) was added to this reaction solution and dissolved thoroughly under vigorous stirring for 60 minutes. After dissolution was confirmed, the reaction was continued at 80°C for 18 hours to obtain a maleimide polymer solution (IBM-1) having a structural unit represented by the following formula (m1). [ka] (Boc represents a tert-butoxycarbonyl group.)

[0097] <Synthesis Example 2> MA-1 (1.87 g, 9.1 mmol) was added to NMP (48.33 g) and stirred at 25°C for 10 minutes. Once dissolution was confirmed, DMAP (0.139 g, 1.14 mmol) was added as a reaction catalyst and stirred for an additional 30 minutes. ISOBAM (3.50 g, 22.7 mmol) was added to this reaction solution and dissolved thoroughly under vigorous stirring for 60 minutes. After dissolution was confirmed, the reaction was continued at 80°C for 18 hours to obtain a maleimide polymer solution (IBM-2) having a structural unit represented by the following formula (m2). [ka]

[0098] <Comparative Synthesis Example 1> ISOBAM (3.50 g) was added to NMP (25.6 g) and dissolved thoroughly with vigorous stirring for 60 minutes. After confirming dissolution, the reaction system was heated at 80°C for 18 hours to obtain a maleic anhydride polymer solution (IBM-3) in which the maleic anhydride groups were not modified. The components of Synthesis Examples 1 and 2 and Comparative Synthesis Example 1 are shown in Table 1 below. [Table 1]

[0099] <Synthesis of polyimide polymer> <Synthesis Example 3> Tetracarboxylic dianhydride D3 (384.45 g, 1715 mmol) and diamine components DA-5 (144.54 g, 437.5 mmol), DA-4 (265.00 g, 350.0 mmol), DA-8 (121.44 g, 612.5 mmol), and DA-9 (83.06 g, 350.0 mmol) were mixed in NMP (2456.1 g) and reacted at 60°C for 12 hours to obtain a polyamic acid solution (PAA-1). NMP (124.62 g) was added to this polyamic acid solution (60.0 g) and diluted to 6.5% by mass. Then, acetic anhydride (21.30 g) and pyridine (3.30 g) were added as imidization catalysts, and the mixture was reacted at 80°C for 5 hours. This reaction solution was poured into methanol (732.28 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a polyimide powder. The imidization rate of this polyimide powder was 72%, and the number average molecular weight was 10,800 and the weight average molecular weight was 41,800. NMP was added to this polyimide powder so that the solid content concentration became 20% by mass, and the mixture was stirred at 70° C. for 12 hours to obtain a polyimide solution (SPI-1).

[0100] <Synthesis Example 4> The diamine components DBA (2.74 g, 18.0 mmol), 3AMPDA (3.27 g, 13.5 mmol), and DA-1 (5.14 g, 13.5 mmol) were mixed and dissolved in NMP (44.59 g). D2 (2.25 g, 9.0 mmol) was added to this solution and reacted at 60 °C for 4 hours. The reaction solution was then cooled with water, and D1 (5.12 g, 26.1 mmol) was added and stirred for 1 hour. Finally, PMDA (1.96 g, 9.0 mmol) was added and stirred at room temperature for 12 hours to obtain a polyamic acid solution (PAA-2). All steps were performed by diluting the reaction solution with NMP solvent to a concentration of 20% by mass. NMP (30.00 g) was added to this polyamic acid solution (30.0 g) and diluted to 10% by mass. Then, acetic anhydride (4.00 g) and pyridine (1.55 g) were added as imidization catalysts, and the mixture was reacted at 70°C for 3 hours. This reaction solution was poured into methanol (229.44 g), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 60°C to obtain a polyimide powder. The imidization rate of this polyimide powder was 75%, and the number average molecular weight was 11,840 and the weight average molecular weight was 37,800. NMP was added to this polyimide powder so that the solid content concentration became 20% by mass, and the mixture was stirred at 70° C. for 12 hours to obtain a polyimide solution (SPI-2).

[0101] <Synthesis Example 5> The diamine components DA-6 (5.20 g, 17.5 mmol), DA-5 (1.73 g, 5.20 mmol), and DA-2 (5.32 g, 12.2 mmol) were mixed and dissolved in NMP (49.10 g). D2 (4.38 g, 17.5 mmol) was added to this solution and reacted at 60 °C for 4 hours. The reaction solution was then cooled with water, and D1 (3.29 g, 16.8 mmol) was added and stirred for 12 hours to obtain a polyamic acid solution (PAA-3). In all steps, the reaction solution was diluted with NMP solvent to a concentration of 20% by mass. The number-average molecular weight of this polyamic acid was 12,540, and the weight-average molecular weight was 41,800.

[0102] <Synthesis Example 6> The diamine components 3AMPDA (3.88 g, 16.0 mmol), DA-3 (3.48 g, 8.8 mmol), and DA-7 (3.41 g, 16.0 mmol) were mixed and dissolved in NMP (43.06 g). D2 (5.00 g, 20.0 mmol) was added to this solution and reacted at 60 °C for 4 hours. The reaction solution was then cooled with water, and D1 (3.77 g, 19.2 mmol) was added and stirred for 12 hours to obtain a polyamic acid solution (PAA-4). In all steps, the reaction solution was diluted with NMP solvent to a concentration of 20% by mass. The number-average molecular weight of this polyamic acid was 10,240, and the weight-average molecular weight was 32,800. The components of Synthesis Examples 3 to 6 are shown in Table 2 below.

[0103] [Table 2]

[0104] [Preparation of polymer composition] (Example 1) The maleimide polymer solution IBM-1 (4.80 g) obtained in Synthesis Example 1 was weighed out and placed in a 20 mL sample tube containing a stirrer, and NMP (2.40 g) and BCS (4.80 g) were added. The mixture was then stirred with a magnetic stirrer for 30 minutes to obtain a maleimide polymer solution, Polymer Composition (A-1). After storing A-1 at -20°C for 1 week, no solid precipitation was observed and the solution was homogeneous. (Example 2) A polymer composition (A-2), which was a maleimide polymer solution, was obtained by the same procedure as in Example 1, except that the maleimide polymer solution IBM-2 was used instead of the maleimide polymer solution IBM-1. After storing A-2 at −20° C. for 1 week, no solid precipitation was observed and it was a homogeneous solution.

[0105] (Example 3) Polyimide solution SPI-1 (0.90 g) obtained in Synthesis Example 3 and polyimide solution SPI-2 (2.10 g) obtained in Synthesis Example 4 were weighed into a 20 mL sample tube containing a stirrer, and NMP (6.00 g) and BCS (6.00 g) were added. The mixture was then stirred with a magnetic stirrer for 30 minutes to obtain polymer composition (A-3), which was a polyimide mixed solution. After storing A-3 at -20°C for 1 week, no solid precipitation was observed and the solution was homogeneous. (Example 4) A polymer composition (A-4), which was a polyamic acid mixed solution, was obtained by the same procedure as in Example 3, except that the polyamic acid solution PAA-3 was used instead of the polyimide solution SPI-1 and the polyamic acid solution PAA-4 was used instead of the polyimide solution SPI-2. After storing A-4 at -20°C for 1 week, no solid precipitation was observed and it was a homogeneous solution. (Example 5) The IBM-3 solution (6.00 g) obtained in Comparative Synthesis Example 1 was weighed into a 20 mL sample tube containing a stirrer, and NMP (4.80 g) and BCS (7.20 g) were added thereto. The mixture was then stirred with a magnetic stirrer for 30 minutes to obtain a maleic acid-based polymer solution, Polymer Composition (B-1). B-1 was stored at -20°C for 1 week, but no solid precipitation was observed, and the solution was homogeneous. The ingredients of Examples 1 to 5 are shown in Table 3 below.

[0106] [Table 3]

[0107] (Example 6) 3.00 g of the solution (A-1) obtained in Example 1 and 7.00 g of the polyimide solution (A-3) obtained in Example 3 were weighed into a 20 mL sample tube containing a stirrer and stirred for 30 minutes with a magnetic stirrer to prepare a polymer composition (C-1). After storing C-1 at -20°C for 1 week, no solid precipitation was observed and it was a homogeneous solution. (Examples 7-11) Polymer compositions (C-2) to (C-4) and (D-1) to (D-2) were prepared in the same manner as in Example 6. The types and mixing ratios of the polymer solutions used in the preparation are listed in Table 4 below.

[0108] [Table 4]

[0109] <Examples 12-19> Liquid crystal alignment films and liquid crystal cells were prepared as follows, and the properties of each prepared liquid crystal cell were evaluated. The results are shown in the table below. In the following examples, Examples 12 to 15 are examples of the present invention, and Examples 16 to 19 are comparative examples.

[0110] <Fabrication of liquid crystal cells> The polymer compositions obtained in Examples 3 to 4 and 6 to 11 were each spin-coated onto the ITO surface of an ITO-attached non-alkali glass substrate (30 mm long, 40 mm wide, 0.7 mm thick) that had been washed with pure water and IPA (isopropyl alcohol), and baked on a hot plate at 70°C for 90 seconds, followed by baking in an infrared heating furnace at 230°C for 20 minutes to produce a coated substrate with a film thickness of 100 nm. Two coated substrates were prepared using the method described above. 4 μm bead spacers were sprayed onto the liquid crystal alignment film surface of one substrate, and then a thermosetting sealant (XN-1500T, manufactured by Kyoritsu Chemical Industry Co., Ltd.) was printed on top of them. Next, the other substrate was bonded to the first substrate with the liquid crystal alignment film facing inward, and the sealant was cured to prepare an empty cell. MLC-3023 (manufactured by Merck) liquid crystal containing a polymerizable compound for PSA was injected into this empty cell using a vacuum injection method to prepare a liquid crystal cell.

[0111] Next, with a DC voltage of 15 V applied to the liquid crystal cell, the liquid crystal cell was irradiated from the outside with a photochemical reaction chemical lamp FHF14UV32A-H (manufactured by Toshiba Lighting & Technology Corporation) for 70 seconds (also referred to as primary PSA treatment). Thereafter, in order to deactivate any unreacted polymerizable compound remaining in the liquid crystal cell, the cell was irradiated with UV (UV lamp: FLR40SUV32 / A-1) for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology Corporation without applying voltage (also referred to as secondary PSA treatment).

[0112] <Evaluation of voltage holding ratio> Using the liquid crystal cell prepared above, a voltage of 1V was applied for 60μs in a 60°C hot air circulating oven, and the voltage was measured after 16.67msec and 1667msec, and the voltage retention rate was calculated to determine how long the voltage was retained. A VHR-1 manufactured by Toyo Corporation was used to measure the voltage retention rate. The voltage retention rates for each material are summarized in Table 5 below.

[0113] <Preparation of a sample for evaluating seal adhesion> The polymer compositions obtained in Examples 3 to 4 and 6 to 11 above were spin-coated onto rectangular glass substrates with transparent electrodes, measuring 30 mm in length, 40 mm in width and 1.1 mm in thickness, and then dried on a hot plate at 70°C for 90 seconds. Thereafter, the substrates were baked in a hot air circulating oven at 230°C for 20 minutes to form liquid crystal alignment films with a thickness of 100 nm. Two substrates were prepared in this way, and 4 μm bead spacers were applied to the liquid crystal alignment film surface of one of the substrates, followed by application of a sealant (723K1 manufactured by Kyoritsu Chemical Industry Co., Ltd.). Next, these substrates were bonded together with the liquid crystal alignment film surfaces facing each other, with an overlap width of 1 cm. The amount of sealant dispensed was adjusted so that the diameter of the sealant after bonding would be 3 mm. The two bonded substrates were then fixed with clips, and a 365 nm wavelength equivalent of 4 J / cm was applied. 2 The adhesive was irradiated with ultraviolet light of 1000 kJ / cm2 and then thermally cured at 120°C for 1 hour to prepare a sample for evaluating adhesion.

[0114] <Evaluation of seal adhesion> The edges of the upper and lower substrates of the adhesion evaluation sample were fixed to the lower part (64 cm) of the three-point bending jig of a tabletop precision universal testing machine (Shimadzu Corporation, AGS-X 500N), and then the substrates were pressed from above the center, and the peel strength (N / mm) was calculated from the force (N) required to peel and the diameter (mm) of the applied seal. The evaluation results are shown in Table 5 below.

[0115] <Evaluation of film hardness> The polymer compositions (C-1) to (C-4) (Examples) and polymer compositions (D-1), (D-2), (A-3), and (A-4) (Comparative Examples) obtained above were spin-coated onto the ITO surface of an alkali-free glass substrate (30 mm long, 40 mm wide, 0.7 mm thick) with ITO. The substrate was baked on a hot plate at 70°C for 90 seconds, and then baked in an infrared oven at 230°C for 20 minutes to produce an alignment agent-coated substrate with a film thickness of 100 nm. The coated substrate surface was rubbed with a rayon cloth in the specified rubbing direction (roll 120 mm, rotation speed 1000 rpm, movement speed 20 mm / sec, push-in depth 0.6 mm), and then observed under an optical microscope to check for scratches on the film. Visually observed scratches were evaluated as "x," and no scratches were evaluated as "o." The evaluation results are shown in Table 5 below.

[0116] [Table 5]

[0117] As shown in Table 5, when the polymer compositions (C-1) to (C-4) of the examples were used, a better voltage holding ratio was observed than when the polymer compositions (D-1), (D-2), (A-3), and (A-4) of the comparative examples were used. As shown in Table 5, when the polymer compositions (C-1) to (C-4) of the examples were used, better seal adhesion and film hardness were exhibited than when the polymer compositions (D-1), (D-2), (A-3), and (A-4) of the comparative examples were used.

[0118] <Evaluation of liquid crystal alignment> Two substrates with liquid crystal alignment films were prepared using the polymer compositions (C-1) to (C-4) obtained in Examples 6 to 9 above. 4 μm spacers were sprayed onto one of the liquid crystal alignment films. A sealant was printed on top of the spacers, and the other substrate was attached so that the liquid crystal alignment film faces the other substrate and the photo-alignment direction is perpendicular. The sealant was then cured to produce an empty cell. Liquid crystal ML-3023 (manufactured by Merck Japan) was injected into this empty cell by the reduced pressure injection method, and the injection port was sealed to obtain a VA liquid crystal cell. This liquid crystal cell was heat-treated at 120°C for 30 minutes, then slowly cooled to room temperature, and the cell was observed. No in-plane alignment defects were observed, and the liquid crystal alignment was good in both cases.

[0119] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2019-221597, filed on December 6, 2019, are hereby incorporated by reference as part of the disclosure of the specification of the present invention.

Claims

1. A polymer composition comprising a polymer (P) having a structural unit represented by the following formula (m-2) and an organic solvent, wherein the total content of the structural units is 5 to 80 mol % based on all structural units of the polymer (P): 【Chemistry 1】 (R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and X represents a structure selected from the following formulae (mx-1) and (mx-2). 【Chemistry 2】 (R １ and R ２ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; D represents a protecting group; each independently represents an alkylene group or an aryl group having 1 to 20 carbon atoms; ２ R 1 and R 2 represent a single bond or an alkylene group having 1 to 20 carbon atoms. ２ In the formula (I), the hydrogen atoms bonded to the alkyl group having 1 to 3 carbon atoms may each independently be substituted with a hydroxy group, —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. * represents a bond.)

2. The polymer composition according to claim 1, wherein the polymer (P) further has a structural unit represented by the following formula (v): 【Transformation 3】 (R ３ , R ４ , R ５ , and R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -OC(=O)-R (wherein R represents an alkyl group having 1 to 6 carbon atoms), -C(=O)-OR (wherein R represents an alkyl group having 1 to 6 carbon atoms), -OR (wherein R represents an alkyl group having 1 to 6 carbon atoms), or a phenyl group.

3. The polymer composition according to claim 1 or 2, wherein the organic solvent is at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone.

4. The polymer composition according to any one of claims 1 to 3, wherein the solid content concentration in the polymer composition is 1 to 10 mass%.

5. The polymer composition according to any one of claims 1 to 4, further comprising a polymer (Q) which is at least one selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid-polyamic acid ester copolymer, polyimide, polyamic, polyorganosiloxane, poly(meth)acrylate, and polyester.

6. 6. The polymer composition according to claim 5, wherein the polyamic acid, polyamic acid ester, or polyamic acid-polyamic acid ester copolymer is obtained by a polymerization reaction between a diamine component and a tetracarboxylic acid component.

7. The diamine component may be p-phenylenediamine, m-phenylenediamine, a diamine having a carboxy group, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4 -aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 2,2'-dimethyl-4,4' 7. The polymer composition according to claim 6, comprising at least one diamine selected from the group consisting of 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, diamines having a terminal photopolymerizable group, diamines having a radical initiation function, diamines having a photosensitizing function that exhibits a sensitizing action upon light irradiation, diamines having a heterocycle, diamines having a diphenylamine skeleton, diamines having the group "-N(D)-" (D represents a protecting group that is cleaved by heating and replaced with a hydrogen atom), diamines having an oxazoline structure, and diamines having a structure in a side chain that exhibits vertical alignment of liquid crystals.

8. The polymer composition according to claim 6 or 7, wherein the tetracarboxylic acid component comprises a tetracarboxylic dianhydride represented by the following formula (3) or a derivative thereof: 【Chemistry 4】 X represents a structure selected from the following (x-1) to (x-13). 【Transformation 5】 (R １ ~R ４ R each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k each independently represent 0 or 1. １ and A ２ each independently represents a single bond, -O-, -CO-, -COO-, phenylene, a sulfonyl group, or an amide group. *1 represents a bond bonded to one acid anhydride group, and *2 represents a bond bonded to the other acid anhydride group. ２ may be the same or different.)

9. A liquid crystal aligning agent comprising the polymer composition according to any one of claims 1 to 8.

10. A liquid crystal alignment film formed by using the liquid crystal aligning agent according to claim 9.

11. A liquid crystal display device comprising the liquid crystal alignment film according to claim 10.

12. A method for producing a liquid crystal display element, comprising: applying the polymer composition according to any one of claims 1 to 8 or the liquid crystal aligning agent according to claim 9 onto a pair of substrates having conductive films to form coating films; arranging the coating films so as to face each other via a layer of liquid crystal molecules to form a liquid crystal cell; and irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates.

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