Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Abstract

Provided are a liquid crystal alignment agent capable of reducing variation (non-uniformity) in twist angle of liquid crystal in the plane of a liquid crystal alignment film even when the amount of light irradiation in alignment treatment by a photo-alignment method is small, a liquid crystal alignment film, and a liquid crystal display element.　The liquid crystal alignment agent contains a polymer (A).　Polymer (A): A polymer is selected from the group consisting of a polyimide precursor having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, and an imidized polymer which is an imidized product of the polyimide precursor, wherein the polymer includes, as the structural unit derived from a tetracarboxylic acid derivative, at least one structural unit selected from the group consisting of a structural unit (a-1Ta) represented by formula (1Ta) and an esterified derivative of the structural unit (a-1Ta), and as the structural unit derived from a diamine, a structural unit (a-1Da1) represented by formula (1Da1) and a structural unit (a-1Da2) represented by formula (1Da2) (the definition of each symbol is as described in the specification).

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element.

[0002] Liquid crystal display devices have traditionally been widely used as display units for personal computers, smartphones, mobile phones, television receivers, etc. Liquid crystal display devices include, for example, 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, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch electric signals supplied to the pixel electrodes. Known methods for driving liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and the VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.

[0003] Currently, the most widely used industrial liquid crystal alignment films are produced by performing an alignment treatment on the surface of a film made of a polymer, typically polyamic acid and / or imidized polyimide, formed on an electrode substrate. In recent years, as liquid crystal display elements have become higher in performance, resolution, and size, photo-alignment methods have been investigated, in which liquid crystal alignment ability is imparted by irradiating polarized radiation. Proposed photo-alignment methods include those utilizing photoisomerization reactions, photo-crosslinking reactions, and photodecomposition reactions (see, for example, Non-Patent Document 1 and Patent Document 1).

[0004] Japanese Patent Application Publication No. 9-297313

[0005] "Liquid Crystal Photo-Alignment Film" Kidowaki, Ichimura, Functional Materials, November 1997, Vol. 17, No. 11, pp. 13-22

[0006] When performing alignment treatment using a photo-alignment method, the amount of light irradiation is a factor that affects energy costs and production speed, so it is preferable to perform alignment treatment with a small amount of light irradiation. However, the inventors' studies have revealed that liquid crystal alignment films that can achieve liquid crystal alignment with a small amount of light irradiation in alignment treatment using a photo-alignment method have a problem in that the twist angle of the liquid crystals within the liquid crystal alignment film is prone to variation (non-uniformity). Therefore, when attempting to increase the screen size of liquid crystal display devices, there is a concern that the liquid crystal alignment may be incomplete in some parts of the resulting liquid crystal alignment film, making it difficult to obtain liquid crystal display devices with excellent contrast and high display quality.

[0007] In view of the above circumstances, the object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film that can reduce the variation (non-uniformity) in the twist angle of the liquid crystal within the liquid crystal alignment film plane even when the amount of light irradiation during alignment treatment by a photo-alignment method is small, the liquid crystal alignment film, and a liquid crystal display element using the liquid crystal alignment film.

[0008] The present inventors have conducted extensive research to achieve the above object, and as a result have found that using a liquid crystal aligning agent containing a polyimide precursor having structural units derived from a specific tetracarboxylic acid derivative and structural units derived from a specific diamine, and / or an imidized polymer, which is an imidized product thereof, is extremely effective for achieving the above object, and have completed the present invention.

[0009] The present invention encompasses the following aspects: A liquid crystal aligning agent characterized by containing the following polymer (A): Polymer (A): At least one polymer selected from the group consisting of polyimide precursors having structural units derived from tetracarboxylic acid derivatives and structural units derived from diamines, and imidized polymers which are imidized products of the polyimide precursors, wherein the structural units derived from the tetracarboxylic acid derivatives are represented by the following formula (1T ａ and at least one structural unit selected from the group consisting of a structural unit (a-1Ta) represented by the following formula (1D ａ１ ) and the structural unit (a-1Da1) represented by the following formula (1Dａ２ The polymer described above, comprising a structural unit (a-1Da2) represented by the formula (a-1Da2). (Formula (1T ａ ) Medium, X ａ represents a tetravalent organic group represented by the above formula (x-1). １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group; R １ ~R ４ At least one of represents a group other than a hydrogen atom as defined above. * represents a bond.) (Formula (1D ａ１ ) ~ (1D ａ２ In the formula (1D), n is an integer of 0 or 1. Each Z independently represents a hydrogen atom or a monovalent organic group. ａ１ ) ~ (1D ａ２ Any hydrogen atom on the benzene ring in

[0010] According to the present invention, it is possible to provide a liquid crystal alignment agent that can obtain a liquid crystal alignment film that can reduce the variation (non-uniformity) in the twist angle of the liquid crystal within the liquid crystal alignment film plane even when the amount of light irradiation in the alignment treatment by the photo-alignment method is small, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element.

[0011] 1 is a schematic cross-sectional view showing an example of an IPS mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, and FIG. 2 is a schematic cross-sectional view showing an example of an FFS mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention.

[0012] A liquid crystal aligning agent containing a specific polymer component, a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film will be described in detail below. However, the following description of the constituent elements is an example of one embodiment of the present invention, and the present invention is not limited to these details. In the following description, examples of "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, "tert-", which means tertiary, is also represented as "t-". "Boc" represents a tert-butoxycarbonyl group, and "*" represents a bond.

[0013] <Polyamic Acid (A)> (Structural Unit Derived from Tetracarboxylic Acid Derivative Contained in Polyamic Acid (A)) The polyamic acid (A), which is one embodiment of the polyimide precursor in the polymer (A) of the present invention, contains a structural unit derived from a tetracarboxylic acid derivative represented by the above formula (1T ａ The polymer (A) may be composed of one or more types of structural units (a-1Ta), and the structural units (a-1Ta) may be composed of one or more types of structural units.

[0014] The above formula (1T ａ ) X ａ represents a tetravalent organic group represented by the above formula (x-1). １ ~R ４ Specific examples of the alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in the above R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and an n-pentyl group. １ ~R ４ Specific examples of the alkenyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, in the above R include a vinyl group, a propenyl group, and a butynyl group, which may be linear or branched. １ ~R ４ Specific examples of the alkynyl group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, in the above R include an ethynyl group, a 1-propynyl group, and a 2-propynyl group. １ ~R ４In the formula (I), examples of the monovalent organic group containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, that contains a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a trifluoromethoxy group, a 2,2,2-trifluoroethyl group, a 2,2,2-trifluoroethoxy group, a pentafluoroethyl group, and a pentafluoropropyl group.

[0015] The above formula (x-1) is preferably at least one selected from the group consisting of the following formulae (x1-1) to (x1-5).

[0016]

[0017] From the viewpoint of suitably achieving the effects of the present invention, the structural unit (a-1Ta) contained in the polyamic acid (A) of the present invention is preferably 60 mol % or more, more preferably 70 mol % or more, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (A). Furthermore, the structural unit (a-1Ta) contained in the polyamic acid (A) of the present invention may be 100 mol % or less, 95 mol % or less, or 90 mol % or less, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (A).

[0018] The polyamic acid (A) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a compound represented by the following formula (2T ａ The structural unit (a-2Ta) may be of one type or of two or more types. (X in the formula ２ａ represents a tetravalent organic group derived from a tetracarboxylic dianhydride other than the tetravalent organic group represented by the above formula (x-1).

[0019] The above formula (2T ａ ) in ２ａ Specific examples of the tetravalent organic group include a tetravalent organic group having an alicyclic structure with five or more members (T ５ａ ), or a tetravalent organic group obtained by removing two acid anhydride groups from the following tetracarboxylic acid dianhydrides (hereinafter, these may be collectively referred to as "other tetracarboxylic acid dianhydrides").

[0020] acyclic aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride or tetracarboxylic acid dianhydrides represented by the following formulae (AL-1) to (AL-7); alicyclic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (provided that the tetravalent organic group (T ５ａ ) and other tetracarboxylic dianhydrides such as those described in JP-A-2010-97188.

[0021] More preferred examples of the other tetracarboxylic dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[0022] The tetravalent organic group (T ５ａ As the tetravalent organic group (T), a tetravalent organic group having a 5- to 8-membered alicyclic structure is preferred, and a tetravalent organic group having a 5- to 7-membered alicyclic structure is more preferred. Note that, when the alicyclic structure to which the acid anhydride group is bonded is a polycyclic structure, the alicyclic structure having 5 or more members means that the number of atoms constituting the ring in each ring contained in the polycyclic structure is 5 or more. Furthermore, the alicyclic structure may be bonded to at least one of the two acid anhydride groups, and may have a chain hydrocarbon structure or an aromatic ring structure together with the alicyclic structure. The tetravalent organic group (T ５ａ ) is preferably a compound represented by the following formula (X ５ａ -1) to (X ５ａ -18). ５ａ ) is, from the viewpoint of suitably obtaining the effects of the present invention, (X ５ａ -1) to (X ５ａ -4) is more preferable.

[0023]

[0024] The polyamic acid (A) has the formula (2T ａThe proportion of the structural units represented by the formula (2T) in the polyamic acid (A) is preferably 40 mol % or less, more preferably 30 mol % or less, based on 1 mol of all structural units derived from the tetracarboxylic acid derivative contained in the polyamic acid (A). ａ The proportion of the structural units represented by the formula (I) may be 5 mol % or more, or 10 mol % or more, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (A).

[0025] (Polyamic Acid Ester (A)) The polyamic acid ester (A), which is one embodiment of the polyimide precursor in the polymer (A) of the present invention, can be obtained by esterifying the carboxyl group of the polyamic acid (A). The polyamic acid ester (A) is preferably a polymer containing an esterified derivative of the structural unit (a-1Ta) and is represented by the formula (1T ａ The polymer (A) is more preferably a polymer having a structure in which at least one of the carboxy groups in the formula (2T ａ The polyamic acid ester can be obtained by a known method, such as [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

[0026] (Polyimide (A)) Polyimide (A) can be obtained by ring-closing (imidizing) a polyimide precursor such as the polyamic acid (A) or polyamic acid ester (A). The imidization ratio referred to in this specification refers to the proportion of imide groups in the total amount of imide groups derived from tetracarboxylic dianhydride or a derivative thereof and carboxyl groups (or derivatives thereof). The imidization ratio does not necessarily have to be 100% and can be adjusted as desired depending on the application and purpose.

[0027] Methods for imidizing the polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, and catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor.

[0028] (Diamine-derived structural unit contained in polymer (A)) The polymer (A) of the present invention contains, as a diamine-derived structural unit, a structural unit represented by the above formula (1D ａ１ ) and the structural unit (a-1Da1) represented by the above formula (1D ａ２ ) The total proportion of the structural unit (a-1Da1) and the structural unit (a-1Da2) is preferably 10 mol% or more, and more preferably 20 mol% or more, relative to 1 mole of all diamine-derived structural units contained in the polymer (A). Furthermore, the total proportion of the structural unit (a-1Da1) and the structural unit (a-1Da2) may be 100 mol% or less, or even 99 mol% or less, relative to 1 mole of all diamine-derived structural units contained in the polymer (A). The proportion of the structural unit (a-1Da1) is preferably 5 mol% or more, and more preferably 10 mol% or more, relative to 1 mole of all diamine-derived structural units contained in the polymer (A). The proportion of the structural unit (a-1Da2) is preferably 5 mol% or more, and more preferably 10 mol% or more, relative to 1 mole of all diamine-derived structural units contained in the polymer (A).

[0029] The above formula (1D ａ１ ) ~ (1D ａ２ In the above formula (I), any hydrogen atom on the benzene ring may be substituted with a monovalent group. Examples of the monovalent group include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms has been substituted with a halogen atom or a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms has been substituted with at least one of the above halogen atoms and a hydroxy group, an alkenyl group having 2 to 3 carbon atoms, an acyl group having 2 to 3 carbon atoms, an alkylsilyl group having 1 to 3 carbon atoms, an alkoxysilyl group having 1 to 3 carbon atoms, a hydroxy group, and a nitrile group.

[0030] The above formula (1D ａ１ ) and (1Dａ２ In the above formula, the monovalent organic group represented by Z is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a methylene group of the hydrocarbon group may be substituted with -O-, -S-, -CO-, -COO-, -COS-, -NR ３ --CO-NR ３ -, -Si(R ３ ) ２ - (However, R ３ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, —SO ２ - or the like; a monovalent group in which at least one hydrogen atom bonded to a carbon atom of the monovalent hydrocarbon group or the monovalent group A is substituted with a halogen atom, a hydroxy group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, an acyl group, or the like; and a monovalent group having a heterocycle. ａ As the monovalent organic group for Z in the above formula (1D), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a t-butoxycarbonyl group is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. ａ In order to preferably obtain the effects of the present invention, two Z's in the formula (I) are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0031] The polymer (A) of the present invention has a diamine-derived structural unit represented by the following formula (1D ａ The structural unit (a-1Da) may be of one type or of two or more types. ａ The monovalent organic group of Z in the formula (1D ａ１ ) and (1D ａ２ ) is synonymous with Z. (Formula (1D ａ ) in Y ａ is expressed by the above formula (1D ａ１ ) and a diamine having hydrogen atoms bonded to both ends of (1D ａ２Z represents a divalent organic group derived from a diamine other than the diamine having hydrogen atoms bonded to both ends of the formula (1D ａ１ ) and (1D ａ２ ) and preferred embodiments are also the same as Z in the above formula (1D ａ１ ) and (1D ａ２ ) is the same as Z in

[0032] Preferred structural units of the structural unit (a-1Da) include other diamines (1) "H-N(Z)-Ar １ -L １ -A-L １’ -Ar １’ -N(Z)-H"-derived structural unit (1D-1), or a structural unit (1D-2) derived from a diamine other than the above-mentioned other diamine (1) (hereinafter also referred to as other diamine (2)). １ , Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring. １ , Ar １’ Any hydrogen atom on the ring may be substituted with a monovalent group. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. L １ , L １’ are each independently a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR- (R represents a hydrogen atom or a monovalent organic group), or -NR-C(=O)- (R represents a hydrogen atom or a monovalent organic group). １ and L １’ is —O—, and A represents a methylene group or a 1,4-butanediyl group, Ar １ , Ar １’ At least one of represents a group other than a 1,4-phenylene group and a divalent organic group in which some of the hydrogen atoms on the phenylene group have been substituted.

[0033] (Other diamines (1)) L of the other diamines (1) １ , L １’Examples of the monovalent organic group for R in -C(=O)-NR- or -NR-C(=O)- include alkyl groups having 1 to 3 carbon atoms, alkoxy groups having 1 to 3 carbon atoms, alkenyl groups having 2 to 3 carbon atoms, acyl groups having 2 to 3 carbon atoms, alkylsilyl groups having 1 to 3 carbon atoms, alkoxysilyl groups having 1 to 3 carbon atoms, and monovalent organic groups in which at least a portion of the hydrogen atoms in these groups have been substituted with at least either halogen atoms or hydroxy groups.

[0034] Ar of the other diamine (1) １ and Ar １’ Examples of the monovalent group that is a substituent for any hydrogen atom on the ring include monovalent groups such as a halogen atom; an alkyl group having 1 to 3 carbon atoms; an alkyl group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with a halogen atom or a hydroxy group; an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with at least one of the above halogen atoms and a hydroxy group; an alkenyl group having 2 to 3 carbon atoms; an acyl group having 2 to 3 carbon atoms; an alkylsilyl group having 1 to 3 carbon atoms; an alkoxysilyl group having 1 to 3 carbon atoms; a hydroxy group, and a nitrile group.

[0035] Ar of the other diamine (1) １ and Ar １’Specific examples of the alkyl group include 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-butyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-t-butyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-butoxy-1,4-phenylene, and 2-fluoro-1,4 a benzene ring which may have a substituent such as 4,4'-biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4,4'-biphenylylene, 2- t-butyl-4,4'-biphenylylene, 2-methoxy-4,4'-biphenylylene, 2-ethoxy-4,4'-biphenylylene, 2-fluoro-4,4'-biphenylylene, 3-methyl-4,4'-biphenylylene, 3-ethyl-4,4'-biphenylylene, 3-propyl-4,4'-biphenylylene, 3-butyl-4,4'-biphenylylene, 3-t-butyl-4,4'-biphenylylene, 3-methoxy-4,4'-biphenylylene, 3-ethoxy-4,4'-biphenylylene biphenyl structures which may have a substituent such as phenylylene, 3-fluoro-4,4'-biphenylylene, 2,2'-dimethyl-4,4'-biphenylylene, 3,3'-dimethyl-4,4'-biphenylylene, 3,3'-biphenylylene, 5-methyl-3,3'-biphenylylene, and 5,5'-dimethyl-3,3'-biphenylylene; and naphthalene rings which may have a substituent such as 1,5-naphthylene, 2,6-naphthylene, and 1-methyl-2,6-naphthylene.

[0036] A in the other diamine (1) is a divalent organic group having 1 to 10 carbon atoms and an alkylene structure. When the alkylene structure has three or more carbon-carbon bonds, any carbon-carbon bond constituting the alkylene structure may be replaced with a carbon-carbon double bond. A is preferably an alkylene group (q0) having 1 to 10 carbon atoms; a divalent organic group (q1) in which —O—, —C(═O)—, —NH—, —O—C(═O)—, or —C(═O)—O— is inserted between the carbon-carbon bonds of the alkylene group; or a divalent organic group (q2) having at least one —NR—C(═O)—NR— (R represents a hydrogen atom or a monovalent organic group) between the carbon-carbon bonds of the alkylene group. Here, the monovalent organic group represented by R in —NR—C(═O)—NR— is preferably L in the diamine (0). １ and L １’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents:

[0037] Preferred examples of (q0), (q1), and (q2) are as follows: *—(CH ２ ) ｎ - *, * - (CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ - *, * - (CH ２ ) ｍ１ -OC(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ - *, * - (CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -OC(=O)-(CH ２ ) ｍ２ - *, * - (CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ -*

[0038] In the above chemical formula, each R independently represents a hydrogen atom or a monovalent organic group. The monovalent organic group is, for example, L of the other diamine (1). １ and L１’ Examples of the structures include those exemplified for R in -C(=O)-NR-, which represents the formula: *-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ In -*, n1 and n2 are each independently an integer of 1 to 6, and the sum of n1 and n2 is 2 to 10. *-(CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ -In *, n1 and n2 are each independently an integer of 1 to 6, and the sum of n1 and n2 is 2 to 9.

[0039] *-L １ -A-L １’ From the viewpoint of suitably obtaining the effects of the present invention, the following embodiments are preferred for -*. In the formulae below, the definitions of m1, m2, n, n', n1, and n2 are the same as in the formulae above. Furthermore, in the formulae below, R represents a hydrogen atom or a monovalent organic group. When two Rs are present, they each independently have the above definition. As the monovalent organic group, the group represented by the formula (H １ ) L １ and L １’ Examples of structures include those exemplified for R in —C(═O)—NR—, which represents ２ ) ｎ -*, -O-(CH ２ ) ｎ -O-*, *-O-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ -O-*, *-C(=O)-(CH ２ ) ｎ -C(=O)-*, *-C(=O)-NR-(CH ２ ) ｎ -O-*, *-OC(=O)-(CH ２ ) ｎ-O-*, *-OC(=O)-(CH ２ ) ｎ -OC(=O)-*, *-OC(=O)-(CH ２ ) ｎ -C(=O)-O-*, *-(CH ２ ) ｍ１ -OC(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ -* *-S-(CH ２ ) ｎ -S-*, *-C(=O)-NR-(CH ２ ) ｎ -NR-C(=O)-*, *-C(=O)-O-(CH ２ ) ｎ -OC(=O)-*, *-(CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -OC(=O)-(CH ２ ) ｍ２ -* *-O-(CH ２ ) ｎ -*, *-S-(CH ２ ) ｎ -*, *-NR-C(=O)-(CH ２ ) ｎ -C(=O)-NR-* *-(CH ２ ) ｎ１ -NR-C(=O)-NR-(CH ２ ) ｎ２ -* Furthermore, from the viewpoint of preferably obtaining the effects of the present invention, *-(CH ２ ) ｎ -*, *-O-(CH ２ ) ｎ -O-*, *-O-(CH ２ ) ｎ - * is preferred.

[0040] The polymer (A) contains, as a diamine-derived structural unit, Y ａ is a divalent organic group having three or more benzene rings, ａ) may contain at least one structural unit represented by the formula: Here, the benzene ring in the "divalent organic group having three or more benzene rings" also includes benzene rings constituting a fused ring. When counting the number of benzene rings in the other diamines (1), a naphthalene ring is counted as having two benzene rings, an anthracene ring is counted as having three benzene rings, and a biphenyl structure is counted as having two benzene rings.

[0041] From the viewpoint of suitably achieving the effects of the present invention, the structural unit (1D-1) preferably has a divalent organic group represented by any one of the following formulae (h1-1) to (h1-14): In formulae (h1-1) to (h1-14), the bonding positions of the benzene ring are preferably the 1st and 4th positions, and the bonding positions of the naphthalene ring are preferably the 2nd and 6th positions. In formula (h1-4), -CH ２ The total number of - is 10 or less. In formulae (h1-7), (h1-8), and (h1-14), -CH ２ The total number of - is 8 or less, and two m's may be the same or different. In addition, the hydrogen atoms on the benzene rings in the following formulae (h1-1) to (h1-14) may be substituted with a methyl group, a methoxy group, or a fluorine atom.

[0042] In one embodiment, the polymer (A) preferably contains the structural unit (1D-1) in an amount of 1 mol % or more, and more preferably 5 mol % or more, based on 1 mol of all diamine-derived structural units contained in the polymer (A). In another embodiment, the polymer (A) preferably contains the structural unit (1D-1) in an amount of 90 mol % or less, and more preferably 80 mol % or less, based on 1 mol of all diamine-derived structural units contained in the polymer (A).

[0043] Examples of the other diamine (2) in the structural unit (1D-2) derived from the other diamine (2) include the following: 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-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, semi-aromatic diamines having a secondary amino group and a primary amino group (preferably 4-(2 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2 ...hydroxy-4,4'-diaminobiphenyl, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-di 4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-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 specific diamines such as (2-methyl)-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, and 2,7-diaminonaphthalene (hereinafter, these may be referred to as specific diamines (2));

[0044] 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate; 4,4'-diamino azobenzene, diaminotolan, 4,4-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4-amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]pro diamines having a photoalignment group, such as aromatic diamines having a cinnamate structure, represented by 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a photopolymerizable group at the terminal, such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone and 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl-3,5-diaminobenzoate; diamines having an amide bond, such as 4,4'-diaminobenzanilide; diamines having a urea bond, such as 1,3-bis(4-aminophenyl)urea; ２ New York Ｄ -NH ２ (Y Ｄ represents a divalent organic group having, in the molecule, -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom); diamines having a thermally eliminable group such as

[0045] 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline dianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane Fluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminobenzyl)benzene; 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl phenyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-(3-(1H-imidazol-1-yl)propyl-3,5-diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-oxazolyl]-benzenamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[benzenamine], 1,4-bis-(4-aminophenyl)pyrrole )-piperazine, 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)benzene-1,3-diamine, or any of the following formulae (z-1) to (z-5): heterocycle-containing diamines such as diamines containing at least one nitrogen atom-containing structure selected from the group consisting of heterocycles containing nitrogen atoms and secondary or tertiary amino groups, typified by diamines having a diphenylamine structure 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-benzenediamine (excluding amino groups derived from -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom); hereinafter, this will also be referred to as a specific nitrogen atom-containing structure; however, the specific nitrogen atom-containing structure is an atomic group other than the two amino groups that participate in the polycondensation reaction);

[0046] 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, 4 ,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4 diamines having a carboxy group such as 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine; diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; metaxylylenediamine, 1 acyclic aliphatic diamines such as 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO2018 / 117239.

[0047]

[0048] D in the above-mentioned -N(D)- is preferably a carbamate-based organic group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a Boc group, etc. A Boc group is particularly preferred from the viewpoints that it is efficiently eliminated by heat, is eliminated at a relatively low temperature, and is discharged as a harmless gas upon elimination.

[0049] The diamine having the thermally detachable group is represented by the following formula (d Ｄａ -1) to (d Ｄａ -8) is preferred. (Formula (d Ｄａ −2), (d Ｄａ -6), (d Ｄａ -7) In the formula, R represents a hydrogen atom or a Boc group.

[0050] In one embodiment, when the polymer (A) used in the present invention has the structural unit (1D-2), it more preferably contains a structural unit derived from the specific diamine (2) from the viewpoint of optimally achieving the effects of the present invention. The structural unit derived from the specific diamine (2) is preferably contained in an amount of 1 mol% or more relative to 1 mol of all diamine-derived structural units contained in the polymer (A). The structural unit derived from the specific diamine (2) is preferably contained in an amount of 90 mol% or less, more preferably 80 mol% or less, relative to 1 mol of all diamine-derived structural units contained in the polymer (A). Furthermore, the polymer (A) may contain, as the structural unit (1D-2), a structural unit derived from a diamine having a thermally labile group from the viewpoint of improving the two-phase separation between the two polymers. The structural unit derived from the diamine having a thermally labile group is preferably contained in an amount of 5 mol% or more relative to 1 mol of all diamine-derived structural units contained in the polymer (A). The structural unit derived from the diamine having the thermally detachable group is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to 1 mol of all structural units derived from the diamine contained in the polymer (A). Furthermore, from the viewpoint of suitably achieving the effects of the present invention, the polymer (A) preferably contains, as the structural unit (1D-2), a diamine other than the diamine having the thermally detachable group, wherein the other diamine is a structural unit derived from a diamine that does not have a side chain group having 3 or more carbon atoms. Here, examples of the diamine having a side chain group having 3 or more carbon atoms include a diamine having the photoalignment group having a side chain group having 3 or more carbon atoms, a diamine having the photopolymerizable group at its terminal and having a side chain group having 3 or more carbon atoms, a diamine having the radical polymerization initiator function and having a side chain group having 3 or more carbon atoms, a diamine having the specific nitrogen atom-containing structure and having a side chain group having 3 or more carbon atoms, a diamine having a steroid skeleton, and a diamine having an alkyl side chain or a cyclic group (aromatic carbon ring, aliphatic hydrocarbon ring) having 3 or more carbon atoms.

[0051] From the viewpoint of suitably achieving the effects of the present invention, the other diamine (1) and the other diamine (2) are preferably diamines selected from the group consisting of other diamines (1) and specific diamines (2) in which A is a 1,2-ethanediyl group. The polymer (A) may have one or more structural units derived from a diamine selected from the group consisting of other diamines (1) and specific diamines (2) in which A is a 1,2-ethanediyl group.

[0052] (Terminal Amino Group) At least a part of the terminals of the polymer (A) contained in the liquid crystal aligning agent of the present invention may contain a non-amino group. A preferred specific example of the non-amino group is a functional group represented by the following structural formula (E). That is, preferably, at least a part of the terminal amino groups of the polymer (A) are modified to have the non-amino group. (In formula (E), Q is a monovalent organic group selected from the following groups (e1) to (e2). * represents a bond.) (e1) An acyclic hydrocarbon group having 1 to 6 carbon atoms. (e2) A monovalent organic group having 2 to 30 carbon atoms and having 1 or 2 carboxy groups (however, the monovalent organic group does not include an acid anhydride group).

[0053] The abundance of terminal amino groups in the polymer (A) may be 60% or less based on all terminals of the polymer (A). The "abundance of terminal amino groups" referred to here, for example, in the case of polyamic acid (A), refers to the proportion of terminals that are amino groups, expressed as a percentage, based on all terminals of the polyamic acid (A). Note that "based on all terminals of the polyamic acid (A)" refers to a case where the total number of amino terminals and non-amino terminals possessed by the polyamic acid (A) is 100%, and includes the total number when any terminal is 0%. The abundance of terminal amino groups is １It can be estimated from the change in peak intensity of the terminal amino group using H-NMR. The abundance of terminal amino groups in the polymer (A) used in the present invention may be 30% or less, 10% or less, or 1% or less. The abundance of terminal amino groups in the polymer (A) used in the present invention may also be 0%. That is, all of the terminals of the polyamic acid (A) used in the present invention may contain the non-amino group.

[0054] The non-amino group is a functional group represented by the structural formula (E). The functional group represented by the structural formula (E) is preferably bonded to a nitrogen atom of the diamine residue. Preferred specific examples of (e1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a vinyl group, an allyl group, and a methallyl group. Preferred specific examples of (e1) include residues derived from acyclic aliphatic dicarboxylic acid anhydrides such as acetic anhydride, acrylic anhydride, methacrylic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, isovaleric anhydride, hexanoic anhydride, or heptanoic anhydride.

[0055] A preferred example of (e2) above is a monovalent organic group having a residue derived from a dicarboxylic acid anhydride and one to two carboxy groups. Specific examples of dicarboxylic acid anhydrides that provide (e2) above include compounds (e2-1) that do not have an alkoxysilane structure and compounds (e2-2) that have an alkoxysilane structure. Specific examples of compound (e2-1) include aromatic or aliphatic cyclic dicarboxylic acid anhydrides such as phthalic anhydride, maleic anhydride, succinic anhydride, allylsuccinic anhydride, itaconic anhydride, trimellitic anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, 4-ethynylphthalic anhydride, or cyclohexene-1,2-dicarboxylic acid anhydride. The aliphatic ring in the aliphatic cyclic dicarboxylic acid anhydride may be a saturated aliphatic ring or an unsaturated aliphatic ring.Specific examples of compound (e2-2) include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-triethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-trimethoxysilylpropyl)phthalic anhydride, 4-(3-triethoxysilylpropyl)phthalic anhydride; (C1 to C6)alkoxydimethylsilyl(C2 to C8)alkyl succinic anhydrides such as 2-(methoxydimethylsilyl)ethyl succinic anhydride, 3-(dimethylmethoxysilyl)propyl succinic anhydride, and 3-(dimethylethoxysilyl)propyl succinic anhydride; 2-(dimethoxymethylsilyl)ethyl succinic anhydride Examples of the di(C1-C6)alkoxymethylsilyl(C2-C8)alkyl succinic anhydride such as succinic acid; tri(C1-C6)alkoxysilyl(C2-C8)alkyl succinic anhydride such as 2-(trimethoxysilyl)ethyl succinic anhydride, 2-(triethoxysilyl)ethyl succinic anhydride, [3-(trimethoxysilyl)propyl]succinic anhydride, or [3-(triethoxysilyl)propyl]succinic anhydride; 4-(3-dimethylmethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylethoxysilylpropyl)phthalic anhydride, or 4-(3-dimethylethoxysilylpropyl)phthalic anhydride.

[0056] <Production of Polyamic Acid> The polyamic acid contained in the liquid crystal aligning agent of the present invention can be produced, for example, by the following method. A polymer having an amic acid structure (polyamic acid) is obtained by reacting a tetracarboxylic dianhydride component, a diamine component, and an amino terminal modifier added as needed in an organic solvent. The polyamic acid is a compound represented by the above formula (1D ａ When the diamine component has a structure represented by the formula -N(Z)-Y ａ The structure of -N(Z)- (Y ａ, Z is defined as above.) is used, and as the tetracarboxylic acid derivative component, a diamine having X ａ (X ａ The definitions of are the same as above.) is used.

[0057] The ratio of tetracarboxylic dianhydride and diamine used in the production of polyamic acid is preferably 0.5 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride per equivalent of the amino group of the diamine, more preferably 0.8 to 1.2 equivalents. As with conventional polycondensation reactions, the closer the equivalent of the acid anhydride group of the tetracarboxylic dianhydride is to 1 equivalent, the higher the molecular weight of the resulting polyamic acid. The reaction temperature in the production of polyamic acid is preferably -20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The production of polyamic acid can be carried out at any concentration, but preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, followed by the addition of an organic solvent.

[0058] At least a portion of the terminals of the polyamic acid (A) may contain the non-amino group. The non-amino group can be formed, for example, by using an amino terminal modifier. Specific preferred examples of the amino terminal modifier include the acyclic aliphatic dicarboxylic acid anhydrides, compound (e2-1), and compound (e2-2). The polyamic acid (A) can be obtained, for example, by the following production method (a), production method (b), production method (c), or a combination of these production methods. Production method (a): A method of polymerizing (polycondensing) a tetracarboxylic dianhydride component, a diamine component, and an amino terminal modifier. Production method (b): A method of reacting a tetracarboxylic dianhydride component with a diamine component to obtain a polymer solution containing a polyamic acid with unmodified amino terminals, and then adding an amino terminal modifier to the polymer solution to react the terminals of the polymer. Production method (c): A method of polymerizing (polycondensing) a tetracarboxylic dianhydride component with a diamine component. In the above-mentioned production method (b), to obtain a polyamic acid having amino terminals, the ratio of the diamine to the tetracarboxylic dianhydride used in the production of the polyamic acid is sufficient as long as the ratio of the diamine used is equal to or greater than the ratio of the tetracarboxylic dianhydride used. Preferably, the ratio of the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 1.0 equivalents per equivalent of the amino group of the diamine, and more preferably, 0.8 to 1.0 equivalents. In the above-mentioned production method (c), the ratio of the tetracarboxylic acid component and the diamine component used in the reaction for producing the polyamic acid is preferably 0.5 to 2 equivalents, and more preferably, 0.8 to 1.2 equivalents, of the acid anhydride group of the tetracarboxylic acid component per equivalent of the amino group of the diamine component. The ratio of the amino terminal modifier used is preferably 40 molar parts or less, and more preferably 30 molar parts or less, per 100 molar parts of the total diamine components used. The proportion of the amino terminal modifier used is preferably 0.1 molar parts or more, more preferably 0.2 molar parts or more, based on 100 molar parts in total of the diamine components used. The temperature when reacting the amino terminal modifier with the polyamic acid may be the same as the reaction temperature in the production of the polyamic acid, or the reaction may be carried out while heating.The heating temperature is preferably 30 to 80° C., more preferably 30 to 60° C. The reaction time is preferably 0.1 to 24 hours, more preferably 1 to 24 hours.

[0059] Specific examples of organic solvents used in the production of the polyamic acid include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. Furthermore, when the polyamic acid to be produced has high solvent solubility, solvents such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether can be used.

[0060] <Solution Viscosity and Molecular Weight of Polymer> From the viewpoint of workability, the polymer (A) used in the present invention preferably has a solution viscosity of, for example, 10 to 1,000 mPa·s when prepared as a 10 to 15% by mass solution. The solution viscosity (mPa·s) of the polymer is a value measured at 25°C using an E-type rotational viscometer on a 10 to 15% by mass polymer solution prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number average molecular weight (Mn) measured by GPC in terms of polystyrene, is preferably 15 or less, more preferably 10 or less. By ensuring that the molecular weight is within this range, good alignment and stability of the liquid crystal display device can be ensured.

[0061] The liquid crystal aligning agent of the present invention may contain a polymer other than the polymer (A). Specific examples of the other polymer include at least one polymer (Q) selected from the group consisting of polyimide precursors other than the polymer (A) and polyimides that are imidized products of the polyimide precursors, polysiloxanes, polyesters, 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 polymers selected from the group consisting of poly(meth)acrylates. From the viewpoint of optimally obtaining the effects of the present invention, the polymer (Q) is more preferably the polymer (B) described below. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, and SMA3000 (manufactured by Cray Valley Corporation), and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.). A specific example of a poly(isobutylene-maleic anhydride) copolymer is ISOBAN-600 (manufactured by Kuraray Co., Ltd.). A specific example of a poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland). One type of other polymer may be used alone, or two or more types may be used in combination. The content of the other polymer is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. In this specification, the term "polymer component" refers collectively to polymers other than polymer (A) and polymer (A) added as needed, contained in the liquid crystal aligning agent. When the polymer contained in the liquid crystal aligning agent is only the polymer (A), the polymer component refers to the polymer (A).

[0062] <Polymer (B)> The liquid crystal aligning agent of the present invention comprises, together with the polymer (A), a polymer (B) selected from the group consisting of a polyimide precursor having a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, and an imidized polymer which is an imidized product of the polyimide precursor, wherein the structural unit derived from the tetracarboxylic acid derivative is represented by the following formula (1T ｂ The polymer (A) and the polymer (B) may contain at least one structural unit selected from the group consisting of the structural unit (b-1Tb) represented by the formula (A) and an esterified derivative of the structural unit (b-1Tb). The polymer (A) and the polymer (B) are different polymers. The polymer (B) may be composed of one type or two or more types. Furthermore, each of the structural units constituting the polymer (B) may be composed of one type or two or more types. (Formula (1T ｂ ) Medium, X ｂ represents a tetravalent organic group derived from a tetracarboxylic dianhydride. ｂ ) in Y ｂ represents a divalent organic group derived from a diamine. Z represents a group represented by the formula (1D ａ１ ) and (1D ａ２ ) is synonymous with Z in

[0063] <Polyamic Acid (B)> (Structural Unit Derived from Tetracarboxylic Acid Derivative Contained in Polyamic Acid (B)) The polyamic acid (B), which is one embodiment of the polyimide precursor in the polymer (B) of the present invention, contains a structural unit derived from a tetracarboxylic acid derivative represented by the above formula (1T ｂ ) has a structural unit (b-1Tb) represented by the above formula (1T ｂ ) X ｂExamples of tetravalent organic groups that give the formula (I) include a tetravalent organic group obtained by removing two anhydride groups (-C(=O)-O-C(=O)-) from an aromatic tetracarboxylic acid dianhydride, a tetravalent organic group obtained by removing two anhydride groups from an acyclic aliphatic tetracarboxylic acid dianhydride, and a tetravalent organic group obtained by removing two anhydride groups from an alicyclic tetracarboxylic acid dianhydride. Here, 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 the 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 have to be composed solely of a chain hydrocarbon structure, and 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 the alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, it is not necessary for the aromatic tetracarboxylic acid dianhydride to be composed solely of an alicyclic structure, and it may also have a chain hydrocarbon structure or an aromatic ring structure as part of it. From the viewpoint of optimally achieving the effects of the present invention, the aromatic tetracarboxylic acid dianhydride is preferably a tetracarboxylic acid dianhydride having a benzene ring. More preferred X ｂThe tetravalent organic group derived from an aromatic tetracarboxylic dianhydride in the above formula is a tetravalent organic group obtained by removing two anhydride groups from the following aromatic tetracarboxylic dianhydrides: pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-perfluoroisopropylidenedi(phthalic anhydride), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2', Aromatic tetracarboxylic acid dianhydrides such as 3,3'-biphenyltetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic) dianhydride, or 4,4'-methylenedi(1,4-phenylene)bis(phthalic) dianhydride. Preferred examples of the acyclic aliphatic tetracarboxylic acid dianhydride include the acyclic aliphatic tetracarboxylic acid dianhydrides exemplified above as other tetracarboxylic acid dianhydrides, and among these, 1,2,3,4-butanetetracarboxylic acid dianhydride is preferred. The alicyclic tetracarboxylic acid dianhydride is a tetracarboxylic acid dianhydride having at least one partial structure selected from the group consisting of a cyclobutane ring structure and a cyclobutene ring structure, or a tetravalent organic group (T ５ａ ) is preferred, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, ５ａ -1) to (X ５ａ Tetracarboxylic acid dianhydrides having a tetravalent organic group represented by any one of the following formulae:

[0064] From the viewpoint of suitably achieving the effects of the present invention, the polyamic acid (B) preferably contains the structural unit (b-1Tb) in an amount of more than 40 mol %, more preferably 50 mol % or more, relative to 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polyamic acid (B). (Polyamic Acid Ester (B)) The polyamic acid ester (B), which is one embodiment of the polyimide precursor in the polymer (B) of the present invention, is obtained by esterifying the carboxy group of the polyamic acid (B). The polyamic acid ester (B) is preferably a polymer containing an esterified derivative of the structural unit (b-1Tb), and is represented by the formula (1T ｂ ) is more preferably a polymer containing a structure in which at least one of the carboxy groups is esterified.

[0065] (Polyimide (B)) Polyimide (B) can be obtained by ring-closing (imidizing) a polyimide precursor such as the polyamic acid (B) or polyamic acid ester (B). The imidization rate does not necessarily have to be 100% and can be adjusted as desired depending on the application and purpose.

[0066] (Diamine-derived structural unit contained in polymer (B)) The polymer (B) of the present invention contains, as a diamine-derived structural unit, a structural unit represented by the following formula (1D ｂ The structural unit (b-1Db) may be of one type or of two or more types. ｂ The monovalent organic group of Z in the formula (1D ａ ) is synonymous with Z. (Formula (1D ｂ Z represents a divalent organic group derived from a diamine. ａ ) is synonymous with Z in

[0067] The above formula (1D ｂ Specific preferred examples of the diamine in the polymer (B) include the diamines exemplified for the polymer (A). ｂis preferably a divalent organic group obtained by removing two amino groups from the semi-aromatic diamine, a diamine having a urea bond (for example, the other diamine (1) in which A is a divalent organic group (q2), or a diamine having a urea bond exemplified in the other diamine (2)), the diamine having an amide bond, the diamine having the specific nitrogen atom-containing structure, the diamine having a carboxy group, or a diamine selected from the group consisting of 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, p-phenylenediamine, and m-phenylenediamine (these are also collectively referred to as specific divalent organic group (b)).

[0068] The polymer (B) is preferably selected from the group consisting of the above-mentioned Y and YB, from the viewpoint of reducing the afterimage caused by the residual DC. ｂ is the specific divalent organic group (b) of the formula (1D ｂ The structural unit (b-1Db) represented by the formula (I) may be contained in an amount of 5 mol % or more, 10 mol % or more, or 20 mol % or more, based on 1 mol of all diamine-derived structural units contained in polymer (B). Furthermore, the structural unit (b-1Db) may be contained in an amount of 100 mol % or less, or 90 mol % or less, based on 1 mol of all diamine-derived structural units contained in polymer (B). Furthermore, from the viewpoint of suitably achieving the effects of the present invention, the structural unit (b-1Db) in polymer (B) is preferably a diamine (2) other than the diamine having a thermally detachable group, wherein the other diamine (2) is a structural unit derived from a diamine that does not have a side chain group having 3 or more carbon atoms.

[0069] The above formula (1D ｂ As the monovalent organic group of Z in the above formula (1D ａ ) and Z in the above formula (I) are examples of the structures shown above.

[0070] In the liquid crystal aligning agent of the present invention, from the viewpoint of reducing afterimages caused by residual DC, the content ratio of the polymer (A) to the polymer (B) in terms of the mass ratio [polymer (A) / polymer (B)] may be 10 / 90 to 90 / 10, 20 / 80 to 90 / 10, or 20 / 80 to 80 / 20.

[0071] <Liquid Crystal Aligning Agent> The liquid crystal aligning agent of the present invention is used to prepare a liquid crystal alignment film and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and a solvent. The content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed. However, from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more relative to the total amount of the liquid crystal aligning agent, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. From the viewpoint of optimally obtaining the effects of the present disclosure, the content ratio of polymer (A) in the liquid crystal aligning agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 50 parts by mass or more, relative to 100 parts by mass of the total polymers contained in the liquid crystal aligning agent. When the liquid crystal aligning agent contains other polymers, the content ratio of polymer (A) is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the polymer components contained in the liquid crystal aligning agent.

[0072] The solvent contained in the liquid crystal aligning agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. , 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 (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

[0073] In addition, the solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also called a poor solvent) that improves the coatability when applying the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the poor solvent to be used in combination are listed below, but are not limited thereto.

[0074] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (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, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol Examples of the lactic acid bacteria include 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 monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether 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, and diisobutyl ketone (2,6-dimethyl-4-heptanone). The content of the poor solvent is preferably 1 to 80 mass %, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass % of the total solvent contained in the liquid crystal aligning agent. The type and content of the poor solvent are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0075] Of these, diisobutyl carbinol, 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 is preferred.

[0076] Preferred solvent combinations of a good solvent and a poor solvent 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, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, and N-methyl-2-pyrrolidone and γ- butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutyl carbinol; 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.

[0077] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the solvent (hereinafter also referred to as additive components). Examples of such additive components include a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compound), an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and a sealant, a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film, or an imidization accelerator for promoting imidization.

[0078] Examples of the crosslinkable compound include at least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and a crosslinkable compound (c-2) having a polymerizable unsaturated group. Specific preferred examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds: Examples of compounds having an epoxy group include 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, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A epoxy resins such as Epikote 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resins such as Epikote 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenols such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). phenol A type epoxy resins, biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom such as tetrakis(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane;N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl) ) cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene and other compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom; isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.); compounds described in paragraph

[0037] of JP-A-10-338880 and compounds described in WO2017 / 170483; Examples of compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aron Oxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl]ether (Aron Oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), and compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO2011 / 132751; Examples of compounds having an oxazoline structure include compounds such as 2,2'-bis(2-oxazoline) and 2,2'-bis(4-methyl-2-oxazoline), polymers and oligomers having an oxazoline group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.), and compounds described in paragraph

[0115] of Japanese Patent Application Laid-Open No. 2007-286597;Examples of compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N',-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, and the compounds described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.), compounds having two or more blocked isocyanate groups described in paragraphs

[0046] to

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

[0119] to

[0120] of WO2015 / 141598; Examples of compounds having a hydroxy group and / or an alkoxy group include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 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 WO2015 / 072554 and paragraph

[0058] of JP2016-118753A, compounds described in JP2016-200798A, and compounds described in WO2010 / 074269A;Examples of crosslinkable compounds having a polymerizable unsaturated group include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-mixture), glycerin tris(meth)acrylate, glycerol 1,3-diglycerolate 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, and hexaethylene glycol mono(meth)acrylate;

[0079] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53

[0105] to 55

[0116] of WO2015 / 060357. Two or more types of crosslinkable compounds may be combined.

[0080] When a crosslinkable compound is used, the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0081] Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N- Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Examples of silane coupling agents include silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.When an adhesion aid is used, the content of the adhesion aid in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Examples of dielectric or conductive substances include monoamines having a nitrogen-containing aromatic heterocycle, such as 3-picolylamine. When a dielectric or conductive substance is used, the content of the dielectric or conductive substance in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0082] The compound for promoting the imidization is preferably a compound having a basic site (e.g., a primary amino group, an aliphatic heterocycle (e.g., a pyrrolidine skeleton), an aromatic heterocycle (e.g., an imidazole ring, an indole ring), or a guanidino group) (excluding the crosslinkable compounds and compounds for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film), or a compound that generates the basic site upon baking. A more preferred example is a compound that generates the basic site upon baking, and preferred specific examples include amino acids in which some or all of the basic sites of the amino acid are protected. Examples of protecting groups for the basic sites of the amino acids include carbamate-based protecting groups such as a Boc group. Specific examples of the amino acids include glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, and ornithine. More preferred specific examples of the compound for promoting imidization include N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine, N-α-(tert-butoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine, etc. The content of the compound for promoting imidization contained in the liquid crystal aligning agent of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0083] (Liquid crystal alignment film) The liquid crystal alignment film of the present invention is formed using the liquid crystal aligning agent of the present invention. The method for producing a liquid crystal alignment film of the present invention includes, for example, applying the liquid crystal aligning agent to a substrate, baking the applied liquid crystal aligning agent, and irradiating the resulting film with polarized radiation. A preferred embodiment of the method for producing a liquid crystal alignment film of the present invention includes, for example, a method for producing a liquid crystal alignment film including a step of applying the liquid crystal aligning agent to a substrate (step (1)), a step of baking the applied liquid crystal aligning agent (step (2)), and, optionally, a step of performing an alignment treatment on the film obtained in step (2) (step (3)).

[0084] <Step (1)> The substrate onto which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and other plastic substrates can also be used. In this case, using a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed is preferable from the viewpoint of simplifying the process. Furthermore, 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 also be used for the electrode. Furthermore, when manufacturing an IPS drive system or FFS drive system liquid crystal display element, a substrate provided with an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate without an electrode are used.

[0085] Examples of a method for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.

[0086] An IPS substrate, which is a comb-teeth electrode substrate used in an IPS system (mode), has a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-teeth pattern, and a liquid crystal alignment film formed on the base material so as to cover the linear electrodes. Meanwhile, an FFS substrate, which is a comb-teeth electrode substrate used in an FFS system (mode), has a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-teeth pattern, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

[0087] FIG. 1 is a schematic cross-sectional view showing an example of an IPS-mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention. In the in-plane switching liquid crystal display element 1 shown in FIG. 1 , liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base 2a, a plurality of linear electrodes 2b formed on the base 2a and arranged in a comb-like pattern, and a liquid crystal alignment film 2c formed on the base 2a to cover the linear electrodes 2b. The counter substrate 4 has a base 4b and a liquid crystal alignment film 4a formed on the base 4b. The liquid crystal alignment film 2c is a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also a liquid crystal alignment film of the present invention. In the in-plane switching liquid crystal display element 1 of FIG. 1 , when a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b, as indicated by electric field lines L.

[0088] Figure 2 is a schematic cross-sectional view showing an example of an FFS-mode in-plane switching liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention. In the in-plane switching liquid crystal display element 1 shown in Figure 2, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped electrode substrate 2 has a base 2d, a surface electrode 2e formed on the base 2d, an insulating film 2f formed on the surface electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-like pattern, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The counter substrate 4 has a base 4b and a liquid crystal alignment film 4a formed on the base 4b. The liquid crystal alignment film 2h is a liquid crystal alignment film of the present invention. The liquid crystal alignment film 4a is also a liquid crystal alignment film of the present invention. In the IPS LCD element 1 shown in FIG. 2, when a voltage is applied to the surface electrodes 2e and the linear electrodes 2g, an electric field is generated between the surface electrodes 2e and the linear electrodes 2g as indicated by electric force lines L.

[0089] <Step (2)> Step (2) is a step of baking the liquid crystal aligning agent applied to the substrate to form a film. After applying the liquid crystal aligning agent to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for evaporating the solvent in the liquid crystal aligning agent can be, for example, 40 to 180°C as the heating means temperature, but may also be 40 to 150°C from the perspective of shortening the process. The baking time is not particularly limited, but is, for example, 1 to 10 minutes, preferably 1 to 5 minutes. When a step of thermally imidizing the amic acid in the polymer is performed in addition to the step of evaporating the solvent, a further baking step can be performed after the solvent evaporation step at a heating means temperature of, for example, 150 to 300°C, preferably 150 to 250°C. The baking time in the thermal imidization step is not particularly limited, but is, for example, 5 to 40 minutes, preferably 5 to 30 minutes. If the film-like substance after baking is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0090] <Step (3)> Step (3) is a step of subjecting the film obtained in step (2) to an alignment treatment. Examples of alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment, with photo-alignment treatment being preferred. Examples of photo-alignment treatment methods include irradiating the surface of the film with polarized radiation in a certain direction, and optionally performing a heat treatment to impart liquid crystal alignment properties (also referred to as liquid crystal alignment ability). As the radiation, ultraviolet light or visible light having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet light having a wavelength of 100 to 400 nm is preferred, and more preferably 200 to 400 nm.

[0091] The radiation dose is 1 to 400 mJ / cm ２ is preferred, and 10 to 300 mJ / cm ２ More preferably, 50 to 250 mJ / cm ２is more preferable. Examples of light sources that can be used for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps. Furthermore, when polarized light is used as the irradiation light, the higher the extinction ratio of polarized light, the higher the anisotropy that can be imparted. For example, in the case of ultraviolet light, the extinction ratio of polarized ultraviolet light is more preferably 10:1 or greater, and even more preferably 20:1 or greater. Furthermore, when irradiating with radiation, in order to improve the liquid crystal alignment, the substrate having the film-like material may be irradiated while being heated at 50 to 250°C. The liquid crystal alignment film prepared in this manner can stably align the liquid crystal molecules in a specific direction. Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can be contact-treated with a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.

[0092] The solvent used in the contact treatment is not particularly limited, as long as it dissolves the decomposition products generated from the film-like material by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among these, water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate are preferred from the viewpoints of versatility and solvent safety. Water, 1-methoxy-2-propanol, and ethyl lactate are more preferred. The solvent may be one type or a combination of two or more types.

[0093] Examples of the contact treatment include immersion treatment and spray treatment (also referred to as spray treatment). The treatment time in these treatments is preferably 10 seconds to 1 hour from the viewpoint of efficiently dissolving the decomposition products generated from the film-like material by irradiation with radiation. In particular, immersion treatment for 1 minute to 30 minutes is more preferable. The solvent used in the contact treatment may be at room temperature or heated, preferably 10 to 80°C, and more preferably 20 to 50°C. In addition, ultrasonic treatment or the like may be performed as necessary from the viewpoint of the solubility of the decomposition products.

[0094] After the contact treatment, it is preferable to perform rinsing (also referred to as "rinsing") with a low-boiling solvent such as water, methanol, ethanol, 2-propanol, acetone, or methyl ethyl ketone, or to perform baking. In this case, either rinsing or baking may be performed, or both may be performed. The baking temperature is preferably 150 to 300°C, more preferably 180 to 250°C, and even more preferably 200 to 230°C. The baking time is preferably 10 seconds to 30 minutes, more preferably 1 minute to 10 minutes. The heat treatment of the coating film irradiated with radiation is preferably performed at 50 to 300°C for 1 minute to 30 minutes, and more preferably at 120 to 250°C for 1 minute to 30 minutes.

[0095] (Liquid Crystal Display Element) The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention. From the viewpoint of obtaining high liquid crystal alignment properties, the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for in-plane switching mode liquid crystal display elements such as IPS mode and FFS mode, and is particularly useful as a liquid crystal alignment film for FFS mode liquid crystal display elements. The liquid crystal display element can be manufactured by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, preparing a liquid crystal cell by a known method, and arranging liquid crystal in the liquid crystal cell. Specifically, the following two methods can be mentioned.

[0096] In the first method, two substrates are placed opposite each other with a gap (cell gap) between them so that their liquid crystal alignment films face each other, and then the peripheries of the two substrates are bonded together using a sealant. A liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant so that it comes into contact with the film surface, and the injection hole is then sealed.

[0097] The second method is called the ODF (One Drop Fill) method. For example, a UV-curable sealant 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 surface. 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.

[0098] In either the first or second method, it is desirable to further heat the coating film 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. When rubbing treatment is performed on the coating film, the two substrates are positioned opposite each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or antiparallel. Similarly, when photoalignment treatment is performed, the substrates are positioned opposite each other so that the alignment directions are at a predetermined angle, for example, perpendicular or antiparallel. Examples of sealing agents that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred.

[0099] The liquid crystal composition is not particularly limited and is a composition containing at least one liquid crystal compound (liquid crystal molecule). It may be a liquid crystal composition having a positive dielectric anisotropy (also called a positive liquid crystal composition or positive liquid crystal) or a liquid crystal composition having a negative dielectric anisotropy (also called a negative liquid crystal composition or negative liquid crystal). However, a negative liquid crystal material is preferred. The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring. It may also contain a compound having two or more rigid moieties (mesogenic skeletons) exhibiting liquid crystallinity within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl or terphenyl structures are connected by an alkyl group). The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase. Furthermore, additives may be further added to the liquid crystal composition in order to improve the liquid crystal alignment properties. Examples of such additives include photopolymerizable monomers such as compounds having a polymerizable group, optically active compounds (e.g., S-811 manufactured by Merck & Co., Inc.), antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, or polymerization inhibitors. Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck & Co., Inc. Examples of negative liquid crystals 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 having a polymerizable group is MLC-3023 manufactured by Merck. Next, polarizing plates are placed. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite the liquid crystal layer.Examples of the polarizing plate 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.

[0100] 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 abbreviations of the compounds used and the methods for measuring the properties are as follows: (Organic solvents) NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve (Tetracarboxylic acid dianhydride) TC-1 to TC-5: Compounds represented by the following formulas (TC-1) to (TC-5), respectively (Diamine) DA-1 to DA-16: Compounds represented by the following formulas (DA-1) to (DA-16), respectively (Terminal Modifier) ​​MA-1: Compound represented by the following formula (MA-1) (Additives) AD-1: Compound represented by the following formula (AD-1) Additive A: N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine Additive B: 3-glycidoxypropyltriethoxysilane

[0101] <Measurement of Viscosity> Measurement was carried out at 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).

[0102] [Polymer Synthesis] <Synthesis Example 1> DA-1 (2.76 g, 12.0 mmol), DA-2 (3.27 g, 12.0 mmol), and NMP (72.8 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.09 g) were added, and the mixture was stirred at room temperature (25°C) for 20 hours to obtain a solution of polyamic acid (PAA-1) with a solids concentration of 12 mass% (viscosity: 170 mPa s). Synthesis Example 2 DA-3 (2.40 g, 12.0 mmol), DA-2 (3.27 g, 12.0 mmol), and NMP (70.4 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (7.83 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-2) with a solids concentration of 12% by mass (viscosity: 237 mPa s). Synthesis Example 3: DA-3 (2.40 g, 12.0 mmol), DA-2 (3.27 g, 12.0 mmol), and NMP (70.4 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25 ° C.) while supplying nitrogen. TC-1 (5.00 g, 22.3 mmol) and NMP (7.83 g) were then added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a polyamic acid solution with a solids concentration of 12% by mass. MA-1 (0.670 g, 6.70 mmol) and NMP (4.91 g) were added to the obtained polyamic acid solution, and the mixture was stirred at room temperature (25 ° C.) for 24 hours to obtain a solution of terminal-modified polyamic acid (PAA-3) (viscosity: 207 mPa s). Synthesis Example 4 DA-1 (1.66 g, 7.21 mmol), DA-2 (0.650 g, 2.39 mmol), DA-4 (1.76 g, 7.20 mmol), DA-5 (2.87 g, 7.20 mmol), and NMP (79.4 g) were placed in a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen.Thereafter, TC-1 (5.08 g, 22.7 mmol) and NMP (8.81 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-4) (viscosity: 182 mPa s) having a solids concentration of 12 mass%. <Synthesis Example 5> DA-1 (1.66 g, 7.21 mmol), DA-2 (0.650 g, 2.39 mmol), DA-4 (1.76 g, 7.20 mmol), DA-5 (2.87 g, 7.20 mmol), and NMP (79.4 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen. Thereafter, TC-1 (5.08 g, 22.7 mmol) and NMP (8.81 g) were added and stirred at room temperature (25° C.) for 20 hours to obtain a polyamic acid solution with a solids concentration of 12% by mass. MA-1 (0.530 g, 5.30 mmol) and NMP (3.89 g) were added to the obtained polyamic acid solution and stirred at room temperature (25° C.) for 24 hours to obtain a solution of terminal-modified polyamic acid (PAA-5) (viscosity: 150 mPa s). <Synthesis Example 6> DA-3 (0.720 g, 3.60 mmol), DA-2 (1.31 g, 4.81 mmol), DA-4 (1.76 g, 7.20 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol) and NMP (73.6 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.17 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-6) having a solids concentration of 12% by mass (viscosity: 164 mPa s). Synthesis Example 7 DA-3 (0.720 g, 3.60 mmol), DA-2 (1.31 g, 4.81 mmol), DA-4 (1.76 g, 7.20 mmol), DA-7 (0.440 g, 3.60 mmol), DA-5 (1.91 g, 4.79 mmol), and NMP (73.9 g) were placed in a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen.Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.21 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-7) with a solids concentration of 12 mass% (viscosity: 173 mPa s). <Synthesis Example 8> DA-1 (1.66 g, 7.21 mmol), DA-2 (0.650 g, 2.39 mmol), DA-8 (1.53 g, 7.21 mmol), DA-5 (2.87 g, 7.20 mmol), and NMP (77.7 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.63 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-8) (viscosity: 180 mPa s) having a solids concentration of 12 mass%. <Synthesis Example 9> DA-3 (0.720 g, 3.60 mmol), DA-2 (1.31 g, 4.81 mmol), DA-4 (1.76 g, 7.20 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol), and NMP (44.2 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen. Thereafter, TC-2 (0.600 g, 2.40 mmol) and NMP (4.91 g) were added and stirred at 40 ° C. for 2 hours. Thereafter, TC-1 (4.52 g, 20.2 mmol) and NMP (33.1 g) were added and stirred at 40 ° C. for 20 hours, thereby obtaining a solution of polyamic acid (PAA-9) with a solids concentration of 12 mass% (viscosity: 158 mPa s). <Synthesis Example 10> DA-9 (7.97 g, 40.0 mmol) and NMP (98.6 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25 ° C.) while feeding nitrogen. Thereafter, after cooling to 15 ° C., TC-3 (6.96 g, 35.5 mmol) and NMP (35.9 g) were added and stirred at room temperature (25 ° C.) for 3 hours. Then, DA-10 (1.98 g, 9.99 mmol) and NMP (17.9 g) were added and dissolved by stirring at room temperature (25° C.).After that, after cooling to 15°C, TC-4 (3.00 g, 9.99 mmol) and NMP (26.9 g) were added and stirred at room temperature (25°C) for 3 hours to obtain a solution of polyamic acid (PAA-10) (viscosity: 165 mPa s) with a solids concentration of 10 mass%. <Synthesis Example 11> DA-9 (11.1 g, 55.9 mmol), DA-11 (2.13 g, 14.0 mmol) and NMP (97.3 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while supplying nitrogen to dissolve the components. Thereafter, TC-5 (19.2 g, 65.2 mmol) and NMP (140 g) were added, and the mixture was stirred at 70°C for 12 hours to obtain a solution of polyamic acid (PAA-11) (viscosity: 120 mPa s) with a solids concentration of 12% by mass. The polyamic acid had an Mn of 9,700 and an Mw of 21,800. <Synthesis Example 12> DA-12 (16.1 g, 54.1 mmol), DA-13 (5.41 g, 36.0 mmol), and NMP (174 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25°C) while supplying nitrogen. After cooling to 15°C, TC-3 (16.9 g, 86.3 mmol) and NMP (43.9 g) were added and stirred at room temperature (25°C) for 2 hours to obtain a solution of polyamic acid (PAA-13) with a solids concentration of 15% by mass (viscosity: 740 mPa s). The polyamic acid had an Mn of 10,933 and an Mw of 28,600. <Synthesis Example 13> DA-9 (3.83 g, 19.2 mmol), DA-11 (0.730 g, 4.80 mmol), and NMP (38.0 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25°C) while supplying nitrogen. Thereafter, TC-2 (1.20 g, 4.80 mmol) and NMP (4.22 g) were added and stirred at 50°C for 2 hours. Thereafter, TC-5 (5.37 g, 18.3 mmol) and NMP (39.4 g) were added, and the mixture was stirred at 70° C. for 12 hours to obtain a solution of polyamic acid (PAA-13) with a solid content of 12% by mass (viscosity: 360 mPa s).Synthesis Example 14: DA-1 (5.53 g, 24.0 mmol) and NMP (69.5 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25 ° C.) while supplying nitrogen. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (7.72 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-14) with a solids concentration of 12 mass% (viscosity: 185 mPa s). Synthesis Example 15: DA-2 (6.54 g, 24.0 mmol) and NMP (76.2 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature (25 ° C.) while supplying nitrogen. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.46 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-15) having a solids concentration of 12% by mass (viscosity: 213 mPa s). <Synthesis Example 16> DA-3 (4.81 g, 24.0 mmol) and NMP (64.7 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (7.19 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-16) having a solids concentration of 12% by mass (viscosity: 219 mPa s). Synthesis Example 17 DA-1 (2.76 g, 12.0 mmol), DA-14 (3.10 g, 12.0 mmol), and NMP (71.7 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (7.97 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-17) with a solids concentration of 12% by mass (viscosity: 213 mPa s). Synthesis Example 18 DA-1 (2.76 g, 12.0 mmol), DA-15 (3.44 g, 12.0 mmol), and NMP (73.9 g) were placed in a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen.Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.22 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-18) having a solids concentration of 12% by mass (viscosity: 256 mPa s). <Synthesis Example 19> DA-1 (2.76 g, 12.0 mmol), DA-16 (3.60 g, 12.0 mmol), and NMP (75.1 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.34 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-19) having a solids concentration of 12% by mass (viscosity: 236 mPa s). Synthesis Example 20 DA-1 (1.66 g, 7.21 mmol), DA-4 (2.35 g, 9.62 mmol), DA-5 (2.87 g, 7.20 mmol), and NMP (79.1 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25 ° C.) while supplying nitrogen. Thereafter, TC-1 (5.11 g, 22.8 mmol) and NMP (8.78 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-20) having a solids concentration of 12 mass% (viscosity: 223 mPa s). Synthesis Example 21 DA-2 (1.96 g, 7.20 mmol), DA-4 (2.35 g, 9.62 mmol), DA-5 (2.87 g, 7.20 mmol), and NMP (80.4 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.93 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-21) having a solids concentration of 12% by mass (viscosity: 187 mPa s).Synthesis Example 22 Into a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, DA-1 (1.66 g, 7.21 mmol), DA-4 (1.76 g, 7.20 mmol), DA-14 (0.620 g, 2.40 mmol), DA-5 (2.87 g, 7.20 mmol) and NMP (79.0 g) were added, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.77 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-22) having a solids concentration of 12% by mass (viscosity: 165 mPa s). Synthesis Example 23 DA-1 (1.66 g, 7.21 mmol), DA-4 (1.76 g, 7.20 mmol), DA-15 (0.690 g, 2.41 mmol), DA-5 (2.87 g, 7.20 mmol) and NMP (79.4 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.82 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-23) having a solids concentration of 12% by mass (viscosity: 188 mPa s). Synthesis Example 24 DA-1 (1.66 g, 7.21 mmol), DA-4 (1.76 g, 7.20 mmol), DA-16 (0.720 g, 2.40 mmol), DA-5 (2.87 g, 7.20 mmol) and NMP (79.6 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.84 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-24) having a solids concentration of 12% by mass (viscosity: 180 mPa s).<Synthesis Example 25> DA-3 (0.720 g, 3.60 mmol), DA-14 (1.24 g, 4.80 mmol), DA-4 (1.76 g, 7.20 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol) and NMP (73.1 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25 ° C.) while supplying nitrogen. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.13 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-25) having a solids concentration of 12% by mass (viscosity: 171 mPa s). <Synthesis Example 26> DA-3 (0.720 g, 3.60 mmol), DA-15 (1.37 g, 4.78 mmol), DA-4 (1.76 g, 7.20 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol) and NMP (74.0 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.22 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-26) having a solids concentration of 12% by mass (viscosity: 176 mPa s). Synthesis Example 27: DA-3 (0.720 g, 3.60 mmol), DA-4 (2.93 g, 12.0 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol) and NMP (72.3 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (8.03 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a solution of polyamic acid (PAA-27) having a solids concentration of 12% by mass (viscosity: 182 mPa s).Synthesis Example 28 Into a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, DA-3 (0.720 g, 3.60 mmol), DA-2 (1.31 g, 4.81 mmol), DA-4 (1.76 g, 7.20 mmol), DA-6 (0.390 g, 3.61 mmol), DA-5 (1.91 g, 4.79 mmol) and NMP (73.6 g) were added, and the mixture was stirred at room temperature (25 ° C.) while supplying nitrogen to dissolve the mixture. Thereafter, TC-1 (5.00 g, 22.3 mmol) and NMP (8.17 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 20 hours to obtain a polyamic acid solution having a solids concentration of 12% by mass. To the resulting polyamic acid solution, MA-1 (0.317 g, 3.17 mmol) and NMP (2.64 g) were added and stirred at room temperature (25° C.) for 24 hours to obtain a solution of terminal-modified polyamic acid (PAA-28) (viscosity: 161 mPa s). Synthesis Example 29: DA-3 (0.720 g, 3.60 mmol), DA-2 (1.31 g, 4.81 mmol), DA-4 (1.76 g, 7.20 mmol), DA-7 (0.440 g, 3.60 mmol), DA-5 (1.91 g, 4.79 mmol), and NMP (70.6 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen. Thereafter, TC-1 (5.06 g, 22.6 mmol) and NMP (11.5 g) were added and stirred at room temperature (25° C.) for 20 hours to obtain a polyamic acid solution with a solids concentration of 12% by mass. MA-1 (0.3058 g, 3.06 mmol) and NMP (2.55 g) were added to the obtained polyamic acid solution and stirred at room temperature (25° C.) for 24 hours to obtain a solution of terminal-modified polyamic acid (PAA-29) (viscosity: 158 mPa s). Synthesis Example 30 DA-1 (0.4145 g, 1.80 mmol), DA-2 (0.6536 g, 2.40 mmol), DA-4 (0.8794 g, 3.60 mmol), DA-5 (0.9564 g, 2.40 mmol), DA-7 (0.2199 g, 1.80 mmol), and NMP (35.92 g) were placed in a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was dissolved by stirring at room temperature (25° C.) while supplying nitrogen.Thereafter, TC-1 (2.5286 g, 11.28 mmol) and NMP (5.53 g) were added, and the mixture was stirred at room temperature (25° C.) for 20 hours to obtain a solution of polyamic acid (PAA-30) with a solids concentration of 12 mass% (viscosity: 148 mPa s). <Synthesis Example 31> DA-9 (7.652 g, 38.40 mmol), DA-12 (2.864 g, 9.60 mmol), and NMP (120.93 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25° C.) while supplying nitrogen to dissolve the polyamic acid. Thereafter, TC-5 (13.55 g, 46.08 mmol) and NMP (55.61 g) were added, and the mixture was stirred at 40° C. for 20 hours to obtain a solution of polyamic acid (PAA-31) with a solid content of 12 mass % (viscosity: 430 mPa s).

[0103] The specifications of the polyamic acids obtained in the above synthesis examples are shown in Tables 1 to 3. In the tables, the numbers in parentheses for the tetracarboxylic acid components represent the amount (parts by mole) of each tetracarboxylic dianhydride used relative to 100 parts by mole of the total amount of the tetracarboxylic acid components used in the polymerization. The numbers in parentheses for the diamine components represent the amount (parts by mole) of each diamine used relative to 100 parts by mole of the total amount of the diamine components used in the polymerization. Polymers (PAA-1) to (PAA-9) and (PAA-28) to (PAA-30) correspond to Polymer (A), and polymers (PAA-10) to (PAA-27) and (PAA-31) correspond to other polymers.

[0104]

[0105]

[0106]

[0107] (Preparation of Liquid Crystal Alignment Agent) <Example 1-1> 13.75 g of the polyamic acid solution (PAA-1) obtained in Synthesis Example 1, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A1). <Example 1-2> 13.75 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 2, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal alignment agent (A2). <Example 1-3> 13.75 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 3, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A3). <Example 1-4> 13.75 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A4). <Example 1-5> 13.75 g of the polyamic acid solution (PAA-5) obtained in Synthesis Example 5, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A5). <Example 1-6> 13.75 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 6, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A6). Example 1-7: 13.75 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A7). Example 1-8: 13.75 g of the polyamic acid solution (PAA-8) obtained in Synthesis Example 8, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A8).Example 1-9: 13.75 g of the polyamic acid solution (PAA-9) obtained in Synthesis Example 9, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 mL Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A9). Example 1-10: 5.50 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4, 9.90 g of the polyamic acid solution (PAA-10) obtained in Synthesis Example 10, 1.65 g of a 1.0 mass% NMP solution of Additive B, 0.83 g of a 10 mass% NMP solution of AD-1, 2.96 g of NMP, 9.00 g of BCS, and 0.17 g of Additive A were added, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (A10). Example 1-11 To a 50 mL Erlenmeyer flask containing a stirrer, 4.13 g of the polyamic acid solution (PAA-4) obtained in Synthesis Example 4, 9.63 g of the polyamic acid solution (PAA-11) obtained in Synthesis Example 11, 1.65 g of a 1.0 mass % NMP solution of Additive B, 0.83 g of a 10 mass % NMP solution of AD-1, 2.96 g of NMP, 9.00 g of BCS, and 0.17 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A11). Example 1-12 Into a 50 mL Erlenmeyer flask containing a stirrer, 5.50 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 6, 6.60 g of the polyamic acid solution (PAA-12) obtained in Synthesis Example 12, 1.65 g of a 1.0 mass % NMP solution of Additive B, 0.83 g of a 10 mass % NMP solution of AD-1, 2.96 g of NMP, 9.00 g of BCS, and 0.17 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A12). Example 1-13 To a 50 mL Erlenmeyer flask containing a stirrer, 4.13 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 6, 9.63 g of the polyamic acid solution (PAA-13) obtained in Synthesis Example 13, 1.65 g of a 1.0 mass % NMP solution of Additive B, 0.83 g of a 10 mass % NMP solution of AD-1, 2.96 g of NMP, 9.00 g of BCS, and 0.17 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A13).Example 1-14 Into a 50 mL Erlenmeyer flask containing a stirrer, 4.50 g of the polyamic acid solution (PAA-6) obtained in Synthesis Example 6, 10.50 g of the polyamic acid solution (PAA-31) obtained in Synthesis Example 31, 1.80 g of a 1.0 mass % NMP solution of Additive B, 1.35 g of a 10 mass % NMP solution of AD-1, 9.71 g of NMP, 12.00 g of BCS, and 0.144 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A14).

[0108] Example 1-15 To a 50 mL Erlenmeyer flask containing a stirrer, 4.50 g of the polyamic acid solution (PAA-28) obtained in Synthesis Example 28, 10.50 g of the polyamic acid solution (PAA-31) obtained in Synthesis Example 31, 1.80 g of a 1.0 mass % NMP solution of Additive B, 1.35 g of a 10 mass % NMP solution of AD-1, 9.71 g of NMP, 12.00 g of BCS, and 0.144 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A15). Example 1-16 To a 50 mL Erlenmeyer flask containing a stirrer, 4.50 g of the polyamic acid solution (PAA-7) obtained in Synthesis Example 7, 10.50 g of the polyamic acid solution (PAA-31) obtained in Synthesis Example 31, 1.80 g of a 1.0 mass % NMP solution of Additive B, 0.90 g of a 10 mass % NMP solution of AD-1, 10.16 g of NMP, 12.00 g of BCS, and 0.144 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A16). Example 1-17 To a 50 mL Erlenmeyer flask containing a stirrer, 4.50 g of the polyamic acid solution (PAA-29) obtained in Synthesis Example 29, 10.5 g of the polyamic acid solution (PAA-31) obtained in Synthesis Example 31, 1.80 g of a 1.0 mass % NMP solution of Additive B, 0.90 g of a 10 mass % NMP solution of AD-1, 10.16 g of NMP, 12.00 g of BCS, and 0.144 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A17). Example 1-18 Into a 50 ml Erlenmeyer flask containing a stirrer, 13.75 g of the polyamic acid solution (PAA-30) obtained in Synthesis Example 30, 7.25 g of NMP, and 9.00 g of BCS were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A18). Example 1-19 To a 50 mL Erlenmeyer flask containing a stirrer, 4.50 g of the polyamic acid solution (PAA-30) obtained in Synthesis Example 7, 10.5 g of the polyamic acid solution (PAA-31) obtained in Synthesis Example 31, 1.80 g of a 1.0 mass % NMP solution of Additive B, 0.90 g of a 10 mass % NMP solution of AD-1, 10.16 g of NMP, 12.00 g of BCS, and 0.144 g of Additive A were added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (A19).

[0109] <Comparative Example 1-1> 13.75 g of the polyamic acid solution (PAA-14) obtained in Synthesis Example 14, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B1). <Comparative Example 1-2> 13.75 g of the polyamic acid solution (PAA-15) obtained in Synthesis Example 15, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B2). <Comparative Example 1-3> 13.75 g of the polyamic acid solution (PAA-16) obtained in Synthesis Example 16, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B3). <Comparative Example 1-4> 13.75 g of the polyamic acid solution (PAA-17) obtained in Synthesis Example 17, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B4). <Comparative Example 1-5> 13.75 g of the polyamic acid solution (PAA-18) obtained in Synthesis Example 18, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B5). <Comparative Example 1-6> 13.75 g of the polyamic acid solution (PAA-19) obtained in Synthesis Example 19, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B6). <Comparative Example 1-7> 13.75 g of the polyamic acid solution (PAA-20) obtained in Synthesis Example 20, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B7). <Comparative Example 1-8> 13.75 g of the polyamic acid solution (PAA-21) obtained in Synthesis Example 21, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B8).<Comparative Example 1-9> 13.75 g of the polyamic acid solution (PAA-22) obtained in Synthesis Example 22, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B9). <Comparative Example 1-10> 13.75 g of the polyamic acid solution (PAA-23) obtained in Synthesis Example 23, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B10). <Comparative Example 1-11> 13.75 g of the polyamic acid solution (PAA-24) obtained in Synthesis Example 24, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B11). <Comparative Example 1-12> 13.75 g of the polyamic acid solution (PAA-25) obtained in Synthesis Example 25, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B12). <Comparative Example 1-13> 13.75 g of the polyamic acid solution (PAA-26) obtained in Synthesis Example 26, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B13). <Comparative Example 1-14> 13.75 g of the polyamic acid solution (PAA-27) obtained in Synthesis Example 27, 7.25 g of NMP, and 9.00 g of BCS were added to a 50 ml Erlenmeyer flask containing a stirrer, and the mixture was stirred for 30 minutes with a magnetic stirrer to obtain a liquid crystal aligning agent (B14).

[0110] The polymers used and their ratios for the liquid crystal aligning agents (A1) to (A19) obtained in Examples 1-1 to 1-19 and the liquid crystal aligning agents (B1) to (B14) obtained in Comparative Examples 1-1 to 1-14 are shown in Tables 4 to 7. In the tables, the values ​​in parentheses indicate the ratio of each polymer to 100 parts by mass of the total amount of the polymers contained in each liquid crystal aligning agent.

[0111]

[0112]

[0113]

[0114]

[0115] [Fabrication of FFS-Driven Liquid Crystal Cells] (Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-6) Liquid crystal cells having the configuration of an FFS-mode liquid crystal display element were fabricated. First, a substrate with electrodes was prepared. The substrate was a rectangular glass substrate measuring 30 mm x 50 mm and 0.7 mm thick. A solid-patterned ITO electrode constituting a common electrode was formed on the substrate as a first layer. A SiN (silicon nitride) film formed by CVD (chemical vapor deposition) was formed as a second layer on the first common electrode. The second SiN film had a thickness of 300 nm, which was thick enough to function as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an ITO film was arranged on the second SiN film as a third layer, forming two pixels, a first pixel and a second pixel, each measuring 10 mm long and 5 mm wide. This electrode-equipped substrate had a structure in which a first-layer common electrode and a third-layer pixel electrode were insulated by a second-layer SiN film. The third-layer pixel electrode had a comb-like shape, with a central portion bent at an interior angle of 160° and multiple 3-μm-wide electrode lines arranged parallel to each other at 6-μm intervals. Each pixel was formed by multiple electrode lines, and had a first region and a second region separated by a line connecting the bent portions. Next, the liquid crystal alignment agents A1 to A3 obtained in Examples 1-1 to 1-3 and the liquid crystal alignment agents B1 to B6 obtained in Comparative Examples 1-1 to 1-6 were filtered through a filter with a pore size of 1.0 μm, and then applied by spin coating to the electrode-equipped substrate (hereinafter referred to as the electrode substrate) and a glass substrate (hereinafter referred to as the counter substrate) having a 4-μm-tall columnar spacer and an ITO film formed on its back surface. After drying on a hot plate at 80°C for 2 minutes, the coating was baked in a hot air circulating oven at 230°C for 20 minutes to form a coating film with a thickness of 100 nm. Polarized ultraviolet light was irradiated onto the coating film surface at 250 mJ / cm through a 254 nm bandpass filter and a polarizer. ２The photo-irradiated film was then washed with ethyl lactate for 5 minutes, rinsed with water for 1 minute, and then baked in an IR oven at 230°C for 30 minutes (hereinafter, this treatment is also referred to as post-photo-alignment treatment (washing and heating)). This resulted in a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was oriented so that the direction dividing the interior angle of the pixel bends was perpendicular to the alignment direction of the liquid crystal. The liquid crystal alignment film formed on the counter substrate was oriented so that the alignment direction of the liquid crystal on the electrode substrate coincided with the alignment direction of the liquid crystal on the counter substrate when the liquid crystal cell was fabricated. The two substrates were combined into a pair, and a sealant (Mitsui Chemicals, Inc., XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the pair, facing each other with the alignment directions of the liquid crystal alignment films at 0°. The bonded substrates were then pressed together and heated in a hot air circulating oven at 150°C for 60 minutes to cure the sealant, producing an empty cell. Positive liquid crystal MLC-3019 (manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left at 23°C overnight before being used for evaluation.

[0116] (Examples 2-4 to 2-13, Comparative Examples 2-7 to 2-14) The liquid crystal alignment agent was changed to the liquid crystal alignment agents A4 to A13 obtained in Examples 1-4 to 1-13, and the liquid crystal alignment agents B7 to B14 obtained in Comparative Examples 1-7 to 1-14, and the photo-alignment post-treatment (washing and heating) was changed to an alignment treatment of baking in an IR oven at 230°C for 30 minutes (hereinafter also referred to as photo-alignment post-treatment (heating)). FFS drive liquid crystal cells were obtained in the same manner as in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-6.

[0117] (Examples 2-14 to 2-19) In addition, FFS drive liquid crystal cells were obtained in the same manner as in Examples 2-4 to 2-13 and Comparative Examples 2-7 to 2-14, except that the liquid crystal alignment agent was changed to the liquid crystal alignment agents A14 to A19 obtained in Examples 1-14 to 1-19.

[0118] [Evaluation of in-plane contrast uniformity] The twist angle variation of the liquid crystal cell was evaluated using an AxoStep manufactured by AXOMETRICS. The liquid crystal cell prepared above was placed on a measurement stage, and the distribution of circular retardance within the pixel plane was measured with no voltage applied, and 3σ, which is three times the standard deviation σ, was calculated. The smaller the 3σ value, the better the in-plane uniformity.

[0119] Tables 8 to 10 below show the liquid crystal alignment agents used in the preparation of FFS cells, the diamine components of the first polymers, the methods of post-photoalignment treatment, and the evaluation results of in-plane contrast uniformity.

[0120]

[0121] It was confirmed that the in-plane uniformity of contrast described in Examples 2-1 to 2-3 was better than that of Comparative Examples 2-1 to 2-6.

[0122]

[0123]

[0124] It was confirmed that the in-plane uniformity of contrast described in Examples 2-4 to 2-19 was better than that of Comparative Examples 2-7 to 2-14.

[0125] By using the liquid crystal aligning agent of the present invention, a liquid crystal alignment film with small variations in the twist angle of the liquid crystal can be obtained even when the amount of light irradiation during alignment treatment by a photoalignment method is small. Therefore, a liquid crystal display element with high display quality can be obtained. These elements are useful in liquid crystal displays for display purposes, light control windows that control the transmission and blocking of light, optical shutters, etc.

[0126] The liquid crystal display element of the present invention can be effectively applied to devices having various functions, and can be used, for example, in liquid crystal televisions, clocks, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, information displays, etc.

[0127] 1: In-plane switching liquid crystal display element, 2: comb-tooth electrode substrate, 2a: substrate, 2b: linear electrode, 2c: liquid crystal alignment film, 2d: substrate, 2e: plane electrode, 2f: insulating film, 2g: linear electrode, 2h: liquid crystal alignment film, 3: liquid crystal, 4: opposing substrate, 4a: liquid crystal alignment film, 4b: substrate, L: electric field line

Claims

1. A liquid crystal aligning agent characterized by containing the following polymer (A): Polymer (A): At least one polymer selected from the group consisting of polyimide precursors having structural units derived from tetracarboxylic acid derivatives and structural units derived from diamines, and imidized polymers which are imidized products of the polyimide precursors, wherein the structural units derived from the tetracarboxylic acid derivatives are represented by the following formula (1T ａ and at least one structural unit selected from the group consisting of a structural unit (a-1Ta) represented by the following formula (1D ａ１ ) and the structural unit (a-1Da1) represented by the following formula (1D ａ２ A polymer comprising a structural unit (a-1Da2) represented by the formula: (Formula (1T ａ ) Medium, X ａ represents a tetravalent organic group represented by the formula (x-1). １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group; R １ ~R ４ At least one of represents a group other than a hydrogen atom as defined above. * represents a bond.) (Formula (1D ａ１ ) ~ (1D ａ２ In the formula (1D), n is an integer of 0 or 1. Each Z independently represents a hydrogen atom or a monovalent organic group. ａ１ ) ~ (1D ａ２ Any hydrogen atom on the benzene ring in 2. The liquid crystal aligning agent according to claim 1, wherein the formula (x-1) is at least one selected from the group consisting of the following formulae (x1-1) to (x1-5): (* represents a bond.) 3. The liquid crystal aligning agent according to claim 1, wherein the total proportion of the structural unit (a-1Da1) and the structural unit (a-1Da2) is 10 mol% or more relative to 1 mol of all structural units derived from diamine contained in the polymer (A).

4. The polymer (A) contains, as a diamine-derived structural unit, the following formula (1D ａ The liquid crystal aligning agent according to claim 1, having a structural unit (a-1Da) represented by the formula (a-1Da). (Formula (1D ａ ) in Y ａ is expressed by the above formula (1D ａ１ ) and a diamine having hydrogen atoms bonded to both ends of the formula (1D ａ２ Z represents a divalent organic group derived from a diamine other than the diamine having hydrogen atoms bonded to both ends of the formula (1D ａ１ ) and formula (1D ａ２ ) is synonymous with Z in 5. The structural unit (a-1Da) is other diamine (1) "H-N(Z)-Ar １ -L １ -A-L １’ -Ar １’ The liquid crystal aligning agent according to claim 4, wherein the structural unit (1D-1) is derived from "-N(Z)-H" or the structural unit (1D-2) is derived from a diamine (2) other than the other diamine (1). １ , Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring. １ , Ar １’ Any hydrogen atom on the ring may be substituted with a monovalent group. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. L １ , L １’ each independently represents a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR- (R represents a hydrogen atom or a monovalent organic group), or -NR-C(=O)- (R represents a hydrogen atom or a monovalent organic group). １ and L １’ is —O—, and A represents a methylene group or a 1,4-butanediyl group, Ar １ , Ar １’ At least one of Z represents a group other than a 1,4-phenylene group and a divalent organic group in which some of the hydrogen atoms on the phenylene group have been substituted. ａ１ ) and formula (1D ａ２ ) is synonymous with Z in 6. The other diamine (2) in the structural unit (1D-2) is 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-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)- ... ) ethylamine, semi-aromatic diamines having secondary and primary amino groups, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diamino Biphenyl, 2-trifluoromethyl-4,4'-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, and 2,7-diaminonaphthalene. The liquid crystal aligning agent according to claim 5, which is at least one selected from the group consisting of 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, and 2,7-diaminonaphthalene.

7. The other diamines (1) in which A in the structural unit (a-1Da) is a 1,2-ethanediyl group, as well as 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-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, and 4-aminobenzyl Amines, 2-(4-aminophenyl)ethylamine, semi-aromatic diamines having secondary amino groups and primary amino groups, 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3-trifluoromethyl fluoro-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-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'-diamino Biphenyl, 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, and 2,7-diaminonaphthalene. The liquid crystal aligning agent according to claim 5, which is at least one selected from the group consisting of diaminonaphthalene.

8. The liquid crystal aligning agent according to claim 1, wherein at least a part of the terminals of the polymer (A) contain a non-amino group, and the non-amino group is a functional group represented by the following structural formula (E): (In formula (E), Q is a monovalent organic group selected from the following groups (e1) to (e2). * represents a bond.) (e1) An acyclic hydrocarbon group having 1 to 6 carbon atoms. (e2) A monovalent organic group having 2 to 30 carbon atoms and having 1 or 2 carboxy groups (however, the monovalent organic group does not include an acid anhydride group).

9. The liquid crystal aligning agent according to claim 8, wherein (e1) is a residue derived from an acyclic aliphatic dicarboxylic acid anhydride.

10. The liquid crystal aligning agent according to claim 8, wherein (e2) is a monovalent organic group having a residue derived from a dicarboxylic acid anhydride and having one or two carboxy groups (however, the monovalent organic group does not contain an acid anhydride group), and the dicarboxylic acid anhydride is selected from a compound (e2-1) not having an alkoxysilane structure or a compound (e2-2) having an alkoxysilane structure.

11. The liquid crystal aligning agent according to claim 10, wherein the compound (e2-1) is an aromatic or aliphatic cyclic dicarboxylic acid anhydride.

12. The compound (e2-2) is 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-triethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-trimethoxysilylpropyl)phthalic anhydride, 4-(3-triethoxysilylpropyl)phthalic anhydride, (C1-6)alkoxydimethylsilyl(C2-8)alkylsuccinic anhydride, di(C1-6)alkoxymethylsilyl(C2-8) The liquid crystal aligning agent according to claim 10, which is selected from alkyl succinic anhydride, tri(C1 to C6)alkoxysilyl(C2 to C8)alkyl succinic anhydride, 4-(3-dimethylmethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-dimethylmethoxysilylpropyl)phthalic anhydride, or 4-(3-dimethylethoxysilylpropyl)phthalic anhydride.

13. The liquid crystal aligning agent according to claim 1, further comprising the following polymer (B): Polymer (B) is a polymer different from polymer (A), and is at least one polymer (B) selected from the group consisting of polyimide precursors having structural units derived from tetracarboxylic acid derivatives and structural units derived from diamines, and imidized polymers which are imidized products of the polyimide precursors, wherein the structural units derived from the tetracarboxylic acid derivatives are represented by the following formula (1T ｂ and at least one structural unit selected from the group consisting of a structural unit (b-1Tb) represented by the following formula (1D) and an esterified derivative of the structural unit (b-1Tb), ｂ A polymer comprising a structural unit (b-1Db) represented by the formula: (Formula (1T ｂ ) Medium, X ｂ represents a tetravalent organic group derived from a tetracarboxylic dianhydride. ｂ ) in Y ｂ represents a divalent organic group derived from a diamine. Z represents a group represented by the formula (1D ａ１ ) and formula (1D ａ２ ) is synonymous with Z in 14. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 13 to a substrate, baking the applied film, and irradiating the resulting film with polarized radiation.

15. The radiation dose is 1 to 400 mJ / cm ２ The method for producing a liquid crystal alignment film according to claim 14, 16. The method for producing a liquid crystal alignment film according to claim 14, wherein the baking temperature is 150 to 250°C.

17. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 13.

18. A liquid crystal display device comprising the liquid crystal alignment film according to claim 17.

19. The liquid crystal display element according to claim 18, which is of an IPS drive system or an FFS drive system.

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