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

Abstract

Provided are: a liquid crystal aligning agent which exhibits excellent printability, has a high voltage retention rate, and can yield a liquid crystal alignment film having a low accumulated charge amount; a liquid crystal alignment film obtained from the liquid crystal aligning agent; and a liquid crystal display element obtained using the liquid crystal alignment film.　The liquid crystal aligning agent is characterized by containing a polymer (A) and component (B).　Polymer (A) 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 imidated polymer that is an imidated product of the polyimide precursor. The polymer contains a structural unit (a-1Ta) represented by formula (1Ta) as the structural unit derived from a tetracarboxylic acid derivative and contains a structural unit (a-1Da) represented by formula (1Da) as the structural unit derived from a diamine.　Component (B) is a compound (B) represented by formula (1). (Meanings of symbols in formula (1Ta) are as defined in the description.) (Meanings of symbols in formula (1Da) are as defined in the description.) Component (B) is a compound (B) represented by formula (1) (meanings of symbols in formula (1) are as defined in the description).

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 obtained from the liquid crystal aligning agent, and a liquid crystal display device using the liquid crystal alignment film.

[0002] Liquid crystal display elements are widely used in a wide range of applications, from small devices such as mobile phones and smartphones to relatively large devices such as televisions and monitors. Various driving methods have been developed, each differing in electrode structure and physical properties of the liquid crystal molecules used. Known liquid crystal display elements use various modes, such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), and fringe field switching (FFS). These liquid crystal display elements generally have a liquid crystal alignment film, which is essential for controlling the alignment state of the liquid crystal molecules. Polyamic acid and its derivatives (e.g., polyimide) are commonly used as materials for the liquid crystal alignment film (see Patent Document 1).

[0003] WO2022 / 220199 publication

[0004] A liquid crystal display element generally comprises a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and common electrodes that apply an electric field to the liquid crystal layer, a liquid crystal alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch electrical signals supplied to the pixel electrodes. In recent years, large-screen, high-resolution liquid crystal display elements have become mainstream, and display element standards with increased pixel counts, such as 4K and 8K, have been developed. Liquid crystal alignment films are required to have the ability to ensure a uniform film thickness even over uneven surfaces on TFT-equipped substrates. Therefore, liquid crystal alignment agents with superior printability compared to conventional liquid crystal alignment agents are required. Furthermore, external stimuli such as light and heat can cause display defects such as image sticking (image sticking of sections and lines), unevenness, or smudges over time. To prevent these display defects, a liquid crystal alignment film with a high voltage retention ratio, which is a prerequisite for long-term reliability of display quality, is required.

[0005] Furthermore, in IPS-type and FFS-type liquid crystal display elements, static electricity is easily accumulated in the liquid crystal cell, and the application of asymmetric voltages generated by driving can also cause charge accumulation in the liquid crystal cell. These accumulated charges can disrupt the alignment of the liquid crystal or affect the display as afterimages, significantly reducing the display quality of the liquid crystal display element. Therefore, liquid crystal alignment films are required to have characteristics that minimize the amount of accumulated charge.

[0006] In view of the above, an object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having excellent printability and a high voltage holding ratio, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.Another object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having a small amount of accumulated charge, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the liquid crystal alignment film.

[0007] The present inventors have conducted extensive research to solve the above problems, and have found that the above problems can be solved by using a specific compound, thereby completing the present invention. The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, or a liquid crystal display element having the liquid crystal alignment film, characterized by containing the following polymers (A) and (B): Polymer (A): A polymer selected from the group consisting of polyimide precursors having structural units derived from a tetracarboxylic acid derivative and structural units derived from a diamine, and imidized polymers which are imidized products of the polyimide precursors, wherein the structural units derived from the tetracarboxylic acid derivative are represented by the following formula (1T ａ As a diamine-derived structural unit, a structural unit (a-1Ta) represented by the following formula (1D ａ The polymer contains a structural unit (a-1Da) represented by the following formula (1): Component (B): Compound (B) represented by the following formula (1): (Formula (1T ａ ) Medium, X ａ represents a tetravalent organic group. Each R independently represents a hydrogen atom or a monovalent organic group. (Formula (1D ａ ) in Yａ is -Ar-L ０ represents a divalent organic group represented by -Ar'-. Ar and Ar' each independently represent a benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle. Any hydrogen atom on the ring of Ar or Ar' may be substituted with a monovalent group. Each Z independently represents a hydrogen atom or a monovalent organic group. L ０ is a single bond, or -L ａ -A-L ａ’ - represents. ａ , L ａ’ 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). A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. However, L ａ and L ａ’ represents —O—, A does not have —C(═O)— or —O—C(═O)—. (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. １ If there are multiple Y １ may be the same or different.) Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4) and a maleimide group. When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and R ｑ１ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *2 in -*2 bonds to a monovalent organic group having a heteroatom-containing group. ３ represents a hydrogen atom or a monovalent organic group. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxy group, or a monovalent organic group.

[0008] In this specification, * represents a bond in all cases. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0009] According to the present invention, a liquid crystal aligning agent capable of producing a liquid crystal alignment film having excellent printability and a high voltage holding ratio, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film are obtained. Furthermore, a liquid crystal aligning agent capable of producing a liquid crystal alignment film having a low amount of accumulated charge, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film are obtained. The mechanism by which the above-mentioned effects of the present invention are achieved is not entirely clear, but the following is thought to be one of the reasons. First, compound (B) has high flexibility and plasticity due to the presence of an alkylene chain and an ester bond in its structure. Furthermore, compound (B) has a relatively small molecular weight, which allows smooth molecular movement within the film during the drying process, making it easy to obtain a smooth coating film. Furthermore, when compound (B) is present in the vicinity of polymer (A) or when compound (B) is introduced into the structure of polymer (A), the ester bond in compound (B) interacts with ionic impurities that cause display defects, resulting in a trapping phenomenon that suppresses the diffusion of impurities, thereby improving the voltage holding ratio. Furthermore, it is believed that the presence of compound (B), which is a compound with a relatively small molecular weight, in the vicinity of polymer (A) or the introduction of compound (B) into the structure of polymer (A) results in a dense coating film, which increases the electrical resistance of the entire film and therefore reduces the amount of accumulated charge.

[0010] <Polymer (A)> The polyimide precursor in the polymer (A) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a structural unit 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.

[0011] (Structural Unit Derived from Tetracarboxylic Acid Derivative Contained in Polymer (A)) The polyimide precursor in the polymer (A) of the present invention contains, as a structural unit derived from a tetracarboxylic acid derivative, a structural unit represented by the above formula (1T ａ ) has a structural unit (a-1Ta) represented by the above formula (1T ｂ ) Xａ Examples 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 an aromatic ring. The acyclic aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not 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 an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, it is not necessary for the structure 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 dianhydride is preferably a tetracarboxylic dianhydride having a benzene ring. More preferred X ａThe 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 1,2,3,4-butanetetracarboxylic acid dianhydride and acyclic aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride or tetracarboxylic acid dianhydrides represented by the following formulas (AL-1) to (AL-7), with 1,2,3,4-butanetetracarboxylic acid dianhydride being particularly preferred.

[0012] The alicyclic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having a cyclobutane ring structure, or a tetravalent organic group having an alicyclic structure of five or more members (T ５ａ A preferred specific example of the tetracarboxylic acid dianhydride having a cyclobutane ring structure is a tetracarboxylic acid dianhydride having a tetravalent organic group represented by the following formula (x-1): (In formula (x-1), R １ ~R ４each 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. * represents a bond.)

[0013] R in 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 ４ In the formula (I), examples of the monovalent organic group containing a fluorine atom and having 1 to 6, preferably 1 to 4, carbon atoms 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.

[0014] The above formula (x-1) is preferably selected from the group consisting of the following formulae (x1-1) to (x1-6).

[0015]

[0016] The tetravalent organic group (T ５ａ), 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.

[0017]

[0018] From the viewpoint of suitably obtaining the effects of the present invention, the structural unit (a-1Ta) contained in the polyimide precursor in the polymer (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 polyimide precursor. Furthermore, the structural unit (a-1Ta) contained in the polyimide precursor in the polymer (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 polyimide precursor.

[0019] The above formula (1T ａ The monovalent organic group for R in the formula (I) is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and the methylene group of the hydrocarbon group may be -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 R in the above formula (1T), 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 obtain the effects of the present invention, the two R's are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0020] The polyimide precursor in the polymer (A) of the present invention has a diamine-derived structural unit represented by the formula (1D ａ ) and the structural unit (a-1Da) represented by the above formula (1D ａ The structural unit (a-1Da) represented by the formula (a-1Da) can be, for example, a diamine represented by the formula (a-1Da) “H—N(Z)-Ar-L ０ -Ar'-N(Z)-H (hereinafter also referred to as "specific diamine"). ａ A preferred embodiment of Z in the above formula (1T ａ The preferred embodiments of R in the above formula (1D) are the same as those in the above formula (1D). ａ ) Y ａ In the formula (1D), Ar and Ar' each independently represent a benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle. Any hydrogen atom on the ring of Ar and Ar' may be substituted with a monovalent group. A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. ａ ) L ａ , L ａ’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).

[0021] L ａ , L ａ’ 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.

[0022] The above formula (1D ａ Examples of the monovalent group that is a substituent for any hydrogen atom on the rings of Ar and Ar′ in the formula (I) 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 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.

[0023] Specific examples of Ar and Ar' 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, 2-fluoro-1, a benzene ring which may have a substituent such as 4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, or 2,3,5,6-tetramethyl-1,4-phenylene; 4,4'-biphenylylene, 2-methyl-4,4'-biphenylylene, 2-ethyl-4,4'-biphenylylene, 2-propyl-4,4'-biphenylylene, 2-butyl-4,4'-biphenylylene, or 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, 3-fluoro-4 biphenyl structures which may have a substituent such as 1,4'-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; naphthalene rings which may have a substituent such as 1,5-naphthylene, 2,6-naphthylene, and 1-methyl-2,6-naphthylene; or the following structures (Ht-1) to (Ht-3), etc.

[0024] The above formula (1D ａ) A is a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. 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 (p0) having 1 to 10 carbon atoms; a divalent organic group (p1) obtained by inserting —O—, —C(═O)—, —NH—, —O—C(═O)—, or —C(═O)—O— between the carbon-carbon bonds of the alkylene group; or a divalent organic group (p2) 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, examples of the monovalent organic group for R in the —NR—C(═O)—NR— include the above-mentioned L ａ and L ａ’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents:

[0025] Preferred examples of (p0), (p1), and (p2) 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 -*

[0026] In the above chemical formula, R represents a hydrogen atom or a monovalent organic group. The monovalent organic group is the same as that of the above L ａ and L ａ’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.

[0027] *-L ａ -A-L ａ’ From the viewpoint of obtaining the effects of the present invention, the following embodiments are preferred for -*. In the following formulae, the definitions of m1, m2, n, n', n1, and n2 are the same as in the formulae above. Furthermore, in the following formulae, 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 above L ａ and L ａ’ 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)-(CH２ ) 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.

[0028] L ０Specific examples of the specific diamine when is a single bond include the following compounds: 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'-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl, 3-fluoro-4,4'-diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl biphenyl, 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, and the like.

[0029] From the viewpoint of suitably achieving the effects of the present invention, the structural unit (a-1Da) preferably has a divalent organic group represented by any one of the following formulae (h1-1) to (h1-18): 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 formulas (h1-7) and (h1-8), -CH ２ The total number of - is 8 or less, and two m's may be the same or different. In addition, hydrogen atoms on the benzene ring, naphthalene ring, or aromatic heterocycle in the following formulae (h1-1) to (h1-13) and (h1-15) to (h1-18) may be substituted with a methyl group, a methoxy group, or a fluorine atom.

[0030] In one embodiment, the polymer (A) preferably contains the structural unit (a-1Da) 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). Also, in one embodiment, the polymer (A) preferably contains the structural unit (a-1Da) in an amount of 100 mol % or less, more preferably 90 mol % or less, and even more preferably 80 mol % or less, based on 1 mol of all diamine-derived structural units contained in the polymer (A).

[0031] The polymer (A) of the present invention contains, as a diamine-derived structural unit, a structural unit represented by the following formula (2D ａ The structural unit (a-2Da) may be of one type or of two or more types. (Formula (2D ａ ) in Y ａ２ represents a divalent organic group derived from a diamine other than the specific diamine. Z has the same meaning as Z in formula (a-1Da) above, and preferred embodiments are also the same as Z in formula (a-1Da) above.

[0032] Specific preferred examples of the other diamines 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-(methylamino)ethyl)aniline.) (Here, semi-aromatic diamine refers to a diamine in which one amino group is bonded to an aromatic ring and the other amino group is not bonded to an aromatic ring.), 4-(2-aminoethyl)aniline, 2-(6-aminonaphthyl)ethylamine, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene;

[0033] 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

[0034] 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)-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 a complex of diamines represented by the following formulas (z-1) to (z-17) and (z-19) to (z-21). ring-containing diamines, or diphenylamine structures such as those of formula (z-18), formula (z-22) to formula (z-23), 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. Diamines (excluding specific diamines) having at least one nitrogen atom-containing structure selected from the group consisting of nitrogen atom-containing heterocycles and secondary or tertiary amino groups, as typified by diamines (excluding amino groups derived from -N(D)- (D represents a protecting group that is eliminated by heating and replaced with a hydrogen atom). Hereinafter, this will also be referred to as a specific nitrogen atom-containing structure. The specific nitrogen atom-containing structure is an atomic group other than the two amino groups that participate in the polycondensation reaction);

[0035] 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.

[0036] (X in (z-13) １３ represents a methyl group or a phenyl group. (In formula (z-19), X １９ represents —C(═O)—, —O—, or —NH—. １９ , R １９’each independently represents a hydrogen atom or a methyl group. ２２ is -CH ２ -, -(CH ２ ) ３ - or -NH-.)

[0037] 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 tert-butoxycarbonyl group (hereinafter also referred to as a "Boc group"), etc. The 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.

[0038] The diamine having the thermally detachable group is represented by the following formula (d Ｄａ -1) to (d Ｄａ -18) is preferred. (Formula (d Ｄａ −2), (d Ｄａ -6), (d Ｄａ -7) In the formula, R represents a hydrogen atom or a Boc group.

[0039] In one embodiment, when the polymer (A) used in the present invention has the structural unit (a-2Da), the structural unit derived from the other diamine preferably accounts for 10 mol% or more, and more preferably 20 mol% or more, of the total structural units derived from the diamine contained in the polymer (A). The structural unit (a-2Da) preferably accounts for 99 mol% or less, and more preferably 95 mol% or less, of the total structural units derived from the diamine contained in the polymer (A). Furthermore, from the viewpoint of improving the two-phase separation between the two types of polymers, the polymer (A) may contain, as the structural unit (a-2Da), a structural unit derived from the diamine having the thermally labile group. The structural unit derived from the diamine having the thermally labile group preferably accounts for 5 mol% or more, of the total structural units derived from the diamine contained in the polymer (A). The structural units derived from the diamine having the thermally detachable group are preferably 40 mol % or less, more preferably 35 mol % or less, and even more preferably 30 mol % or less, based on 1 mol of all structural units derived from the diamine contained in the polymer (A).

[0040] <Production of Polyimide Precursor or Polyimide> In the polymer (A) contained in the liquid crystal aligning agent of the present invention, ａ A polyamic acid in which at least one of R in the formula (1D) is a hydrogen atom 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 with a diamine component. 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.) A tetracarboxylic dianhydride having the following structure is used. For detailed synthesis methods of polyimide precursors and polyimides, see, for example, WO2015 / 012368.

[0041] In producing the polyimide precursor or polyimide of the present invention, a terminal-capping polymer may be produced using a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, a diamine component containing a diamine, and an appropriate terminal-capping agent. The terminal-capping polymer has the effect of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion properties between the sealant and the liquid crystal alignment film.

[0042] Examples of the terminals of the polyimide precursor or polyimide in the present invention include an amino group, a carboxy group, an acid anhydride group, or a group derived from an end-capping agent described below. The amino group, carboxy group, and acid anhydride group can be obtained by a conventional condensation reaction or by blocking the terminals with the following end-capping agents.

[0043] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, maleic anhydride, succinic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; and chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride. monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; and isocyanates having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0044] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, and more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0045] The polystyrene-equivalent weight average molecular weight (Mw) of the polyimide precursor and polyimide measured by gel permeation chromatography (GPC) 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 polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, more preferably 10 or less. By having the molecular weight within this range, good liquid crystal alignment properties can be ensured in liquid crystal display elements.

[0046] <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.

[0047] 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 selected from the group consisting of polyimide precursors other than the polymer (A) and polyimides that are imidized products of the polyimide precursors (hereinafter also referred to as "polymer (Q)"), 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).

[0048] <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) are different polymers. The polymer (B) may be composed of one type or two or more types. Furthermore, the structural units constituting the polymer (B) may each 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 ａ ) has the same meaning as Z in the above formula (1T ａ ) is synonymous with Z in

[0049] <Polymer (B)> (Structural Unit Derived from Tetracarboxylic Acid Derivative Contained in Polymer (B)) 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 ｂ Examples of the tetravalent organic group that gives the formula (I) include tetravalent organic groups obtained by removing two anhydride groups (—C(═O)—O—C(═O)—) from the tetracarboxylic dianhydrides exemplified for the polymer (A).

[0050] In order to suitably obtain the effects of the present invention, the polymer (B) preferably contains the structural unit (b-1Tb) in an amount of more than 40 mol %, and more preferably 50 mol % or more, based on 1 mol of all structural units derived from tetracarboxylic acid derivatives contained in the polymer (B).

[0051] (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

[0052] The above formula (1D ｂ Specific preferred examples of the diamine in the polymer (B) include the diamines exemplified for the polymer (A). ｂ is preferably a divalent organic group obtained by removing two amino groups from the semi-aromatic diamine, a diamine having a urea bond (for example, a specific diamine in which A is a divalent organic group (q2), or a diamine having a urea bond exemplified in the above-mentioned other diamines), a diamine having an amide bond, a diamine having a specific nitrogen atom-containing structure, a 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)").

[0053] 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 relative to 1 mol of all diamine-derived structural units contained in the polymer (B). The content of the structural unit (b-1Db) may be 100 mol % or less, or 90 mol % or less, relative to 1 mol of all diamine-derived structural units contained in the polymer (B).

[0054] 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.

[0055] 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.

[0056] <Component (B)> The liquid crystal aligning agent of the present invention contains a compound (B) represented by the following formula (1). (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’ L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group.１ If there are multiple Y １ may be the same as or different from each other. * represents Ar １ or Ar １’ Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4) and a maleimide group. When formula (1) has a plurality of (q1) to (q4), the plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and multiple R ｑ１ each independently represents a hydrogen atom or a monovalent organic group. ｑ１ may be the same or different. ｑ１ ) ２ *2 in -*2 is bonded to a monovalent organic group having a heteroatom-containing group. Examples of the heteroatom-containing group include a hydroxy group, a carboxy group, and an epoxy group. In formula (q2), R ３ represents a hydrogen atom or a monovalent organic group. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxy group, or a monovalent organic group. When Q or Q' represents a maleimide group, Q or Q' is bonded to Ar via a nitrogen atom in the maleimide group. １ or Ar １’ and combine.

[0057] R in the above formula (q1) １The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ６ --CO-NR ６ -, -Si(R ６ ) ２ - (However, R ６ When a plurality of groups are present, each group independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.), —SO ２ - or the like (R １ｂ ), the monovalent hydrocarbon group, or the monovalent group (R １ｂ and a monovalent group in which at least one hydrogen atom bonded to a carbon atom of R is replaced with a substituent (x), and a monovalent group having a heterocycle. １ is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ -*2. R in the above formula (q1) is bonded to the nitrogen atom via any one of the linking groups ２、 R in formula (q2) ３ , R in formula (q3) ４ and R in formula (q4) ５ The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ６ --CO-NR ６ -, -Si(R ６ ) ２ - (However, R ６ When a plurality of groups are present, each group independently represents a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms.), —SO ２ - or the like (R ｂ ), the monovalent hydrocarbon group, or the monovalent group (R ｂ and monovalent groups having a heterocycle, in which at least one hydrogen atom bonded to a carbon atom of the formula (I) is replaced with a substituent (x). Examples of the substituent (x) include a halogen atom, a hydroxy group, a nitro group, an amino group, a mercapto group, a nitroso group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, and a sulfo group.

[0058] In the above formula (2), Y １ and Y ２ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and examples of the divalent hydrocarbon group include, but are not limited to, a linear or branched alkylene group, —CH═CH—, a phenylene group, or a cyclohexylene group. １ and Y ２ From the viewpoint of suitably achieving the effects of the present invention, Y is preferably a hydrocarbon group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably an alkylene group having 2 or 4 carbon atoms. Some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups, and the halogen atoms substituting the hydrogen atoms in the divalent hydrocarbon group are preferably fluorine atoms. １ If there are multiple Y １ may be the same as or different from each other. L represents -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-. When multiple Ls are present, the multiple Ls may be the same as or different from each other. However, it is preferable that at least one L represents -O-C(=O)- or -C(=O)-O-, and at least two Ls represent -O-C(=O)- or -C(=O)-O-. n represents an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and even more preferably an integer of 2 or 4.

[0059] The group "*-(Y １ -L) ｎ -Y ２ More preferred examples of "-*" include the following structures: *-(CH ２ ) ｐ -OC(=O)-(CH ２ ) ｑ -C(=O)-O-(CH ２ ) ｒ - *, * - (CH ２ ) ｐ -C(=O)-O-(CH ２ ) ｑ-OC(=O)-(CH ２ ) ｒ - *, * - (CH ２ ) ｎ１ -OC(=O)-(CH ２ ) ｎ２ -C(=O)-O-(CH ２ ) ｎ３ -OC(=O)-(CH ２ ) ｎ４ -C(=O)-O-(CH ２ ) ｎ５ - *; * - (CH ２ ) ｎ１ -C(=O)-O-(CH ２ ) ｎ２ -OC(=O)-(CH ２ ) ｎ３ -C(=O)-O-(CH ２ ) ｎ４ -OC(=O)-(CH ２ ) ｎ５ *: In the above structure, p, q, and r are each independently an integer of 1 to 6. n1 to n5 are each independently an integer of 1 to 6. However, when n1 to n5 are each an integer of 1 to 6, the total number of carbon atoms in the divalent hydrocarbon group is 20 or less.

[0060] A preferred example of formula (q1) is *-NH-C(=O)-R Ｏ (R Ｏ represents a monovalent organic group bonded to the carbon atom of a carbonyl group via an oxygen atom; *—NH—C(═O)—R Ｎ (However, R Ｎ represents a monovalent organic group bonded to the carbon atom of a carbonyl group via a nitrogen atom; *—NH—C(═O)—R Ｃ (However, R ｃ represents a monovalent organic group bonded to the carbon atom of the carbonyl group via a carbon atom; *—NH—(CH ２ ) ｎ -OH (n is an integer of 1 to 6); or the following formulae (q1-a) to (q1-d): R ０Preferred examples of R include organic groups in which one hydrogen atom has been removed from the hydroxy group of an alcohol compound, an oxime compound, or a phenol compound. Ｎ Preferred examples of R include organic groups in which one hydrogen atom has been removed from the nitrogen atom of a nitrogen-containing compound such as a lactam compound, an amine compound, a pyrazole compound, an imidazole compound, or an imide compound. Ｃ Preferred examples of the alkyl group, the alkenyl group, the organic group in which one hydrogen atom has been removed from the carbon atom of an active methylene compound, or -(CH ２ ) ｎ -COOH (n is an integer of 1 to 6).

[0061] Examples of the alcohol compounds include saturated alcohols such as methanol, ethanol, propanol, butanol (preferred examples include n-butanol, i-butanol, sec-butanol, and tert-butanol), cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate; acyclic unsaturated alcohols such as allyl alcohol; and alcohols having an aromatic ring such as benzyl alcohol and 9-fluorenylmethanol. Examples of the oxime compounds include acetoxime, formaldoxime, cyclohexaneoxime, methyl ethyl ketoneoxime, cyclohexanoneoxime, and benzophenoneoxime. Examples of the lactam compounds include ε-caprolactam and γ-butyrolactam. Examples of the phenol compounds include phenol, naphthol, cresol, xylenol, and halogen-substituted phenols. Examples of the amine compounds include primary amines and secondary amines. The amine compound may be any of aromatic amines, aliphatic amines, and alicyclic amines, and may be a monoalkylamine (methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.), a dialkylamine (preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, methylethylamine, methylpropylamine, ethylpropylamine) group, a H ２ N (Boc), HN (Boc) ２Examples of the active methylene compounds include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compounds include pyrazole, methylpyrazole, and dimethylpyrazole. Examples of the imidazole compounds include imidazole, 1-methylimidazole, 1-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compounds include maleimide, succinimide, phthalimide, and derivatives thereof.

[0062] R in formula (q2) ３ Preferred specific examples of the alkyl group include a hydrogen atom; a linear alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 6 carbon atoms; a carbamate-based organic group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a Boc group, and the like; a glycidyl group; an epoxycyclohexylmethyl group (preferably a 2,3-epoxycyclohexylmethyl group or a 3,4-epoxycyclohexylmethyl group); a group having an oxetane ring represented by the following formula (q2-a); and an N-hydroxysuccinimide ester group. (In formula (q2-a), R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms.)

[0063] R in formula (q3) ４ Preferred examples of the group include a hydroxy group; ｑ３ (R ｑ３ represents an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, or a group having an aromatic ring (for example, a benzyl group, a 9-fluorenylmethyl group, etc.); a glycidyl group; an epoxycyclohexylmethyl group (preferably a 2,3-epoxycyclohexylmethyl group or a 3,4-epoxycyclohexylmethyl group); and a group having an oxetane ring represented by the above formula (q2-a).

[0064] Preferred examples of formula (q4) include a hydroxyalkyl group having 1 to 6 carbon atoms (preferably a methylol group) and an aliphatic carboxy group having 2 to 6 carbon atoms.

[0065] Examples of the monovalent group substituting a hydrogen atom on the benzene ring, the biphenyl structure, or the naphthalene ring in Ar and Ar′ of the above formula (1) include a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, a cyano group, and a nitro group.

[0066] The compound (B) is preferably at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q2-1) to (q2-3), (q3-1) to (q3-3), and (q4-1) to (q4-2):

[0067] The content of the compound (B) represented by the above formula (1) in the liquid crystal aligning agent of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the polymer (A).

[0068] <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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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 a crosslinking compound, excluding compound (B)), 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 sealing agent, 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.

[0075] 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;

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] (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)).

[0081] <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.

[0082] 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.

[0083] <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.

[0084] <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.

[0085] 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. The heat treatment of the coating film irradiated with the radiation is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.

[0086] (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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] The liquid crystal composition is not particularly limited and is a composition containing at least one liquid crystal compound (liquid crystal molecule), and may be either a liquid crystal composition having a positive dielectric anisotropy (also referred to as a positive liquid crystal composition or positive liquid crystal) or a liquid crystal composition having a negative dielectric anisotropy (also referred to as a negative liquid crystal composition or negative liquid crystal). However, a negative liquid crystal composition 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, or may contain a compound having two or more rigid moieties (mesogenic skeletons) exhibiting liquid crystallinity in 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.

[0091] 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 GBL: γ-butyrolactone BCS: butyl cellosolve THF: tetrahydrofuran (Tetracarboxylic acid dianhydrides) CA-1 to CA-4: Compounds represented by the following formulas (CA-1) to (CA-4), respectively (Diamine) DA-1 to DA-8: Compounds represented by the following formulas (DA-1) to (DA-8), respectively (Additives) AD-1 to AD-11: Compounds represented by the following formulas (AD-1) to (AD-11), respectively Among the above additives, AD-3 to AD-7, AD-10 and AD-11 are included in the range of specific additives corresponding to compound (B) of the present application.

[0092] (Reaction Reagent) Boc ２ O: di-tert-butyl dicarbonate SAH: succinic anhydride Ac ２ O: acetic anhydride

[0093] <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).

[0094] <Measurement of molecular weight> Measurement was carried out using the following room temperature GPC (gel permeation chromatography) apparatus under the following conditions, and Mn and Mw were calculated as polyethylene glycol oxide equivalent values. GPC apparatus: GPC-101 (manufactured by Resonaq (formerly Showa Denko) K.K.), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonaq (formerly Showa Denko) K.K.) connected in series, Column temperature: 50°C, Eluent: N,N-dimethylformamide (containing lithium bromide monohydrate (LiBr.H) as an additive), ２o-Phosphoric acid (o-Phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), flow rate: 1.0 mL / min. Standard sample for preparing a calibration curve: EasiVial PEG / PEO polyethylene glycol oxide PL2080-0201 (molecular weight: about 1,500, about 4,000, about 13,000, about 30,000, about 70,000, about 130,000, about 500,000, about 1,000,000, about 1,500,000) (GL Sciences).

[0095] [Synthesis of Monomer] DA-8 is a novel compound not disclosed in any literature. The product in Monomer Synthesis Example 1 below is １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for １ H)

[0096] <Monomer Synthesis Example 1: Synthesis of DA-8> 2-(4-nitrophenoxy)ethanol (50.0 g, 273 mmol) was charged with THF (600 g), 4-dimethylaminopyridine (DMAP, 16.6 g, 13.6 mmol), and succinic anhydride (34.1 g, 341 mmol), and the mixture was stirred at 50°C. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl, 59.8 g, 312 mmol) and 1,4-butanediol (11.7 g, 130 mmol) were charged into the resulting solution, and the mixture was stirred at room temperature (25°C) for 3 hours. After completion of the reaction, water (1.5 kg) was added to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. THF (300 g) was added to the crude crystals, and the mixture was heated and stirred at 65°C. After cooling to room temperature, methanol (1.5 kg) was added and the mixture was recrystallized. The crystals were filtered off and the resulting crystals were dried to obtain DA-8-1 (yield: 60.4 g, 97.2 mmol, 75%). １ H-NMR (500MHz) in DMSO-d ６δ (ppm) = 8.21 (d, J = 9.2 Hz, 4H), 7.17 (d, J = 9.2 Hz, 4H), 4.37 (q, 8H), 3.99 (s, 4H), 2.58 (m, 8H), 1.57 (m, 4H). To the DA-8-1 (60.3 g, 97.2 mmol) obtained above, THF (1.2 kg) was added and the mixture was purged with nitrogen. Then, carbon-supported palladium (5% Pd carbon powder (hydrated product) K type, manufactured by N.E. Chemcat Corporation) (6.0 g) was added and the mixture was purged with nitrogen again. A Tedlar bag containing hydrogen was attached, and the mixture was stirred at room temperature for 4 days. After completion of the reaction, the carbon-supported palladium was removed by passing it through a membrane filter, and the filtrate was completely concentrated to precipitate crude crystals. The crude crystals were washed with isopropyl alcohol (240 g) and stirred at room temperature. The crystals were filtered off and the resulting crystals were dried to obtain DA-8 (yield: 44.8 g, 79.9 mmol, 82%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 6.65 (d, J = 8.9 Hz, 4H), 6.50 (d, J = 8.9 Hz, 4H), 4.62 (s, 4H) 4.27 (m, 4H), 4.00 (m, 8H), 2.57 (m, 8H), 1.59 (m, 4H).

[0097] [Synthesis of Additives] AD-3 to AD-7, AD-10 and AD-11 are novel compounds not disclosed in the literature, and the products in the following Additive Synthesis Examples 1 to 8 are １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for １ H)

[0098] Additive Synthesis Example 1: Synthesis of AD-3 NMP (35.0 g) was added to DA-6 (5.00 g, 12.0 mmol) and the mixture was purged with nitrogen. ２O (7.35 g, 72.0 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, the above solution was slowly added dropwise to methanol (300 g) to cause recrystallization, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-3 (yield: 4.99 g, 9.96 mmol, 83%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.76 (s, 2H), 7.46 (d, J = 8.6Hz, 4H), 6.87 (d, J = 8.6Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.23 (t, 4H), 2.00 (s, 6H), 1.54 (m, 4H).

[0099] Additive Synthesis Example 2: Synthesis of AD-4 NMP (8.50 g) was added to DA-6 (1.50 g, 3.60 mmol) and the mixture was purged with nitrogen. SAH (1.08 g, 10.8 mmol) dissolved in NMP (5.0 g) was then added and the mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After completion of the reaction, the above solution was slowly added dropwise to methanol (300 g) to allow recrystallization, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-4 (yield: 1.42 g, 2.30 mmol, 64% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.1 (br, 2H), 9.80 (s, 2H), 7.48 (d, J = 9.1Hz, 4H), 6.87 (d, J = 9.1 Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.51 (m, 8H), 2.33 (t, 4H), 1.54 (m, 4H).

[0100] Additive Synthesis Example 3: Synthesis of AD-5 Under a nitrogen atmosphere, DA-6 (3.33 g, 8.00 mmol), Boc ２O (3.50 g, 16.0 mmol) and THF (33 g) were added and reacted at room temperature with stirring. After the reaction was completed, the solvent was removed using an evaporator, 30 g of isopropyl alcohol was added, and the precipitated solid was filtered off. This was dried to obtain AD-5 (3.50 g, 5.67 mmol, yield 71%, pink-white crystals). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.11 (s, 2H), 7.32 (d, 4H), 6.83 (d, 4H), 4.30 (t, 4H), 4.10 (t, 4H), 2,32 (s, 4H), 1.54 (s, 4H), 1.46 (s, 18H).

[0101] Additive Synthesis Example 4: Synthesis of AD-6 THF (18.4 g) was added to DA-8 (3.60 g, 6.42 mmol) and purged with nitrogen. Then, Boc ２ O (8.41 g, 38.5 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (3.70 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator. The precipitated solid was dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-6 (yield: 3.57 g, 4.69 mmol, 73%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.12 (s, 2H), 7.34 (d, J = 8.5Hz, 4H), 6.84 (d, J = 9.1Hz, 4H), 4.31 ( t, 4H), 4.10 (t, 4H), 4.00 (t, 4H), 2.57 (m, 8H), 1.57 (m, 4H), 1.46 (s, 18H).

[0102] Additive Synthesis Example 5: Synthesis of AD-7 THF (16 g) was added to DA-7 (2.00 g, 5.20 mmol) and purged with nitrogen. Then, Boc ２0 (2.62 g, 12.0 mmol) was added, and the mixture was stirred at room temperature for 2 days to react. After completion of the reaction, water (100 g) was added in an ice bath to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. Methanol (50 g) was added to the crude crystals, and the mixture was heated and stirred at 70°C, allowed to cool at room temperature, and then recrystallized. The crystals obtained were filtered off and dried to obtain AD-7 (yield: 2.12 g, 3.62 mmol, 70%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.23 (s, 2H), 7.37 (d, J = 8.5Hz, 4H), 7.11 (d, J = 8.5Hz, 4H), 4.17 (t, 4H), 2.79 (t, 4H), 2.23 (m, 4H), 1.46 (m, 22H).

[0103] Additive Synthesis Example 6: Synthesis of AD-8 THF (20.4 g) was added to DA-5 (3.60 g, 18.0 mmol) and purged with nitrogen. Then, Boc ２ O (8.24 g, 37.8 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (3.63 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator. The precipitated solid was dispersed in toluene (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-8 (yield: 5.54 g, 13.9 mmol, 77% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.02 (s, 2H), 7.70 (s, 1H), 7.26 (d, J = 8.1Hz, 4H), 6.89 (d, J = 8.9Hz, 4H), 1.46 (s, 18H).

[0104] Additive Synthesis Example 7: Synthesis of AD-10 4-(Benzyloxy)phenol (16.0 g, 80.0 mmol), sodium hydroxide (32 g, 800 mmol), and pure water (288 g) were added and heated to 80°C. 2-Chloroethanol (64.4 g, 800.0 mmol) was slowly added dropwise using a dropping funnel. After the dropwise addition was completed, the mixture was stirred at 80°C for 3 hours. After confirming the completion of the reaction by NMR, ethyl acetate (960 g) was added to extract the organic layer, which was then separated and washed with saturated aqueous sodium chloride solution (320 g) and pure water (320 g). The organic layer was extracted and concentrated, and then heptane (160 g) was added to perform slurry washing. The precipitated crystals were filtered off, washed with heptane, and then dried under reduced pressure at 40°C to obtain powder crystals (AD-10-1) (yield: 18.7 g, 76.5 mmol, 95% yield, white crystals). To the AD-10-1 (14.6 g, 59.6 mmol) obtained above, THF (218 g), 4-dimethylaminopyridine (DMAP, 0.710 g, 5.81 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl, 26.8 g, 139.6 mmol) were added and stirred at room temperature for 10 minutes. Adipic acid (4.24 g, 29.1 mmol) was then added and stirred overnight at room temperature (25°C). Then, pure water (600 g) was added to allow crystallization. The resulting crystals were filtered off, washed with pure water and methanol, and then dried under reduced pressure at 40°C to obtain powder crystals (AD-10-2) (yield: 15.4 g, 25.6 mmol, 88% yield, white crystals). To the AD-10-2 (15.4 g, 25.6 mmol) obtained above, THF (154 g) was added and the mixture was purged with nitrogen. Then, carbon-supported palladium (5% by mass Pd carbon powder (50% water content) K type, manufactured by N.E. Chemcat Corporation) (1.54 g) was added and the mixture was purged with nitrogen again. A hydrogen Tedlar bag was attached, and the mixture was stirred at room temperature (23°C) for 21 hours. After the reaction was completed, the catalyst was filtered off, the mixture was concentrated, and heptane (90 g) was added and stirred at room temperature for 30 minutes. The precipitated crystals were filtered under reduced pressure, the cake was washed with heptane and methanol, and then dried under reduced pressure at 40° C. to obtain powder crystals (AD-10) (yield: 10.3 g, 24.6 mmol, 96%, white crystals). １ H-NMR (500MHz) in DMSO-d６ :8.93 (2H, s), 6.73 (4H, d), 6.57 (4H, d), 4.27 (4H, t), 4.04 (4H, t), 2.32 (4H, t), 1.53 (4H, q)

[0105] Additive Synthesis Example 8: Synthesis of AD-11 4-Dimethylaminopyridine (DMAP, 0.015 g, 0.12 mmol) and THF (10 g) were added to AD-10 (1.0 g, 2.39 mmol) and stirred at room temperature. ２ A solution of 1.15 g of methyl 2,4-dichlorobenzofuran (5.0 g) in THF (1.15 g, 5.3 mmol) was added dropwise to the mixture, and the mixture was allowed to react at room temperature for 2 hours. After the reaction, the mixture was concentrated, and IPA (10 g) was added and stirred at room temperature for 30 minutes. The precipitated crystals were filtered under reduced pressure, washed with IPA, and then dried under reduced pressure at 40°C to obtain powder crystals (AD-11) (yield: 1.3 g, 2.0 mmol, 86% yield, white crystals). １ H-NMR (500MHz) in DMSO-d ６ :7.10 (4H, d), 6.95 (4H, d), 4.32 (4H, t), 4.16 (4H, t), 2.32 (4H, t), 1.53 (4H, q), 1.47 (18H, s)

[0106] [Polymer Synthesis] <Synthesis Example 1> DA-1 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while supplying nitrogen. Thereafter, CA-1 (1.69 g, 7.54 mmol) and NMP (12.4 g) were added, and the mixture was stirred at 40°C for 18 hours to obtain a solution of polyamic acid (A-1) with a solids concentration of 12% by mass (viscosity: 225 mPa s). The Mn of this polyamic acid was 10,382 and the Mw was 32,874.

[0107] Synthesis Example 2 DA-2 (0.977 g, 4.00 mmol), DA-5 (0.797 g, 4.00 mmol), and NMP (10.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (1.50 g, 6.00 mmol) and NMP (8.30 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (0.494 g, 1.68 mmol) and NMP (2.80 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-2) with a solids concentration of 15% by mass (viscosity: 304 mPa s). The Mn of this polyamic acid was 9,284, and the Mw was 26,834.

[0108] Synthesis Example 3: DA-1 (9.74 g, 34.0 mmol), DA-3 (1.37 g, 4.01 mmol), DA-4 (1.11 g, 1.99 mmol), and NMP (106 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 while introducing nitrogen. Thereafter, CA-1 (7.89 g, 35.2 mmol) and NMP (41.0 g) were added, and the mixture was stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-3) with a solids concentration of 12% by mass (viscosity: 210 mPa s). The Mn of this polyamic acid was 10,521, and the Mw was 32,302.

[0109] Synthesis Example 4 DA-5 (10.2 g, 51.0 mmol), DA-2 (8.31 g, 34.0 mmol), and NMP (135 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (13.8 g, 55.2 mmol) and NMP (47.6 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (7.45 g, 25.3 mmol) and NMP (41.1 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-4) with a solids concentration of 15% by mass (viscosity: 309 mPa s). The Mn of this polyamic acid was 10,357, and the Mw was 26,452.

[0110] Synthesis Example 5 DA-1 (1.58 g, 5.50 mmol) and NMP (16.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while supplying nitrogen. Thereafter, CA-4 (1.15 g, 5.28 mmol) and NMP (8.10 g) were added, and the mixture was stirred at 50°C for 18 hours, yielding a solution of polyamic acid (A-5) with a solids concentration of 12% by mass (viscosity: 239 mPa s). The Mn of this polyamic acid was 10,094 and the Mw was 33,198.

[0111] The types and amounts of the tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 5 are shown in Table 1. In Table 1, the numerical values ​​for the tetracarboxylic acid components and diamine components represent the proportions (parts by mole) of each compound used relative to 100 parts by mole of the total amount of the diamine components used in the synthesis of each polyamic acid.

[0112]

[0113] Synthesis Example 6 To the polyamic acid solution A-3 (20 g), 0.11 g (1.13 mmol) of SAH was added and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (A-6) having a non-amino terminal structure.

[0114] [Preparation of Liquid Crystal Alignment Agent] Example 1 To the solution (1.63 g) of the polyamic acid (A-1) obtained in Synthesis Example 1, the solution (3.90 g) of the polyamic acid (A-2) obtained in Synthesis Example 2, NMP (0.90 g), GBL (6.36 g), BCS (6.00 g), AD-1 (1 mass% GBL solution, 0.78 g), AD-2 (10 mass% NMP solution, 0.39 g), and AD-3 (0.04 g) were added, and the mixture was stirred at room temperature for 2 hours, thereby obtaining a liquid crystal aligning agent (AL-1) of the present invention.

[0115] <Examples 2 to 10 and Comparative Examples 1 to 4> By carrying out the same operation as in Example 1 above, except that the type and amount of polymer solution, solvent, and additive used were changed as shown in Table 2, the liquid crystal aligning agent (AL-2) to (AL-10) of Examples 2 to 10 of the present invention and the liquid crystal aligning agent (AL-C1) to (AL-C4) of Comparative Examples 1 to 4 were obtained.

[0116]

[0117] In Table 2, the numerical values ​​for Polymer 1, Polymer 2, Additive 1, Additive 2, Specific Additive, and Other Additives represent the proportions (parts by mass) of each polymer solid content and additive relative to 100 parts by mass of the total polymer components.

[0118] [Preparation of Liquid Crystal Cell] <Preparation of ECB-Type Liquid Crystal Cell> A liquid crystal cell having the configuration of an ECB-mode liquid crystal display element was prepared. First, a substrate with electrodes was prepared. The substrate was a glass substrate measuring 30 mm x 40 mm and 0.7 mm thick. ITO electrodes with a thickness of 35 nm were formed on the substrate, and the electrodes were in a stripe pattern spaced 40 mm vertically and 10 mm horizontally. Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm and then applied to the substrate with electrodes prepared above by spin coating. The resulting solution was then dried on a hot plate at 80°C for 2 minutes and then baked in an infrared oven at 230°C for 20 minutes to form a coating film with a thickness of 60 nm. This liquid crystal alignment film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm) using a rayon cloth (HY-5318 manufactured by Hyperflex Corporation). Subsequently, the film was washed by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then the film was dried at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with this liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed onto the liquid crystal alignment film surface of one of the substrates. After that, a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was printed around the periphery, leaving the liquid crystal injection port, and the other substrate was bonded to the other substrate with the rubbing direction in the opposite direction and the film surfaces facing each other. Subsequently, the substrate was heated at 150 ° C for 60 minutes to harden the sealant and produce an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. The obtained liquid crystal cell was then heated at 120°C for 1 hour and allowed to stand at 23°C overnight before being used for evaluation.

[0119] <Fabrication of FFS-Driven Liquid Crystal Cell> A liquid crystal cell with the configuration of an FFS-mode liquid crystal display element was 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 deposited by CVD (chemical vapor deposition) was formed on the first common electrode as a second layer. The second SiN film had a thickness of 300 nm, which served as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an ITO film as a third layer was disposed on the second SiN film. Two pixels, a first pixel and a second pixel, were formed, each measuring 10 mm long and 5 mm wide. This electrode-equipped substrate had a structure in which the first common electrode and the third pixel electrode were insulated by the second SiN film. The pixel electrode of the third layer had a comb-like shape with the central portion bent at an interior angle of 160° and multiple electrode lines, each 3 μm wide, arranged parallel to each other at intervals of 6 μm. One pixel was formed by multiple electrode lines and had a first region and a second region separated by a line connecting the bent portions.

[0120] Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm, and then spin-coated onto the electrode-attached substrate (hereinafter referred to as the "electrode substrate") and a glass substrate (hereinafter referred to as the "counter substrate") having a 4 μm-high columnar spacer with an ITO film formed on the back surface. After drying for 2 minutes on a hot plate at 80 ° C, it was baked for 20 minutes in a hot air circulating oven at 230 ° C to form a coating film with a thickness of 60 nm. This coating film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm) using a rayon cloth (HY-5318 manufactured by Hyperflex). The substrate was then ultrasonically cleaned in pure water for 1 minute, water droplets were removed by air blowing, and the substrate was dried at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was subjected to an alignment treatment so that the direction dividing the interior angle of the pixel bend was parallel to the liquid crystal alignment direction. The liquid crystal alignment film formed on the counter substrate was also subjected to an alignment treatment so that the alignment direction of the liquid crystal on the electrode substrate was aligned 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 XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the other substrate, facing each other with the alignment directions of the liquid crystal alignment films aligned at 0°. The bonded substrates were then pressed together and heated for 60 minutes in a hot air circulating oven at 150°C to cure the sealant, producing an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into this empty cell using a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left overnight at 23°C before being used for evaluation.

[0121] [Evaluation of Liquid Crystal Cell Characteristics] The characteristics of the ECB-type liquid crystal cell and the FFS-type liquid crystal cell prepared above were evaluated as follows.

[0122] <Evaluation of Charge Accumulation Amount by AC Drive> The FFS-driven liquid crystal cell prepared above was placed between two polarizing plates arranged with their polarization axes perpendicular to each other. With the pixel electrode and the common electrode shorted and at the same potential, an LED backlight was irradiated from below the two polarizing plates. The angle of the liquid crystal cell was adjusted so that the luminance of the LED backlight transmitted through the two polarizing plates was minimized. Next, a 60 Hz AC voltage was applied to the liquid crystal cell, and the VT curve (voltage-transmittance curve) was measured. The AC voltage at which the relative transmittance was 23% was calculated as the driving voltage. For image retention evaluation, the liquid crystal cell was driven for 60 minutes by applying a 60 Hz AC voltage at which the relative transmittance was 100%. Then, an AC voltage at which the relative transmittance was 23% was applied, and the DC voltage was swept to measure the applied voltage at which display flicker was minimized. The absolute value of the applied voltage at which display flicker was minimized was defined as the charge accumulation amount. The smaller the charge accumulation amount, the better. The evaluation of the afterimage according to the above-mentioned method was carried out under a temperature condition in which the temperature of the liquid crystal cell was 45°C.

[0123] <Evaluation of voltage holding ratio after backlight durability test> The ECB-type liquid crystal cell was placed under a high-intensity backlight (light source: LED, brightness: 30000 cd / m) with a surface temperature of 50°C. ２ ) for 96 hours. Next, a voltage of 1 V was applied to the liquid crystal cell at a temperature of 60°C for 60 μsec, and the voltage after 167 msec was measured, and the voltage retention rate was calculated to indicate how much voltage was retained. The higher the voltage retention rate, the better the results.

[0124] [Evaluation of Coatability] The liquid crystal alignment agent obtained above was applied by spin coating to an ITO substrate measuring 100 mm x 100 mm and having a thickness of 1.1 mm. After drying on a hot plate at 80°C for 2 minutes, the substrate was baked in a hot air circulating oven at 230°C for 20 minutes to obtain a substrate with a liquid crystal alignment film having a thickness of 60 nm. When the substrate with the liquid crystal alignment film was observed with the naked eye, if the coating surface was uniform and free of unevenness, it was rated as "good," and if unevenness was visible on the coating surface, it was rated as "poor."

[0125] Table 3 shows the evaluation results of the charge storage amount, voltage holding ratio, and coatability using each of the liquid crystal alignment agents of Examples 1 to 10 and Comparative Examples 1 to 4. The numbers in parentheses for the polymer components and additives represent the blending ratio (parts by mass) of each polymer solid content and additive when the total content of the polymer solid content is 100 parts by mass.

[0126]

[0127] As shown in Table 3, the liquid crystal alignment film obtained from the liquid crystal alignment agent containing the specific diamine and the specific additive was superior in all of the charge storage capacity, voltage holding ratio, and coatability compared to the liquid crystal alignment film obtained from the liquid crystal alignment agent containing the specific diamine and neither the specific additive nor other additives (Comparison between Examples 1 to 5 and 8 to 10 and Comparative Example 1, and Examples 6 and 7 and Comparative Example 4). On the other hand, when the specific diamine was used and other additives were added, one of the charge storage capacity, voltage holding ratio, and coatability was improved compared to the liquid crystal alignment film obtained from the liquid crystal alignment agent containing the specific diamine and neither the specific additive nor other additives, but not all of them were superior (Comparison between Comparative Examples 2 and 3 and Comparative Example 1).

[0128] The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used in various liquid crystal display elements, typified by liquid crystal display elements of an IPS drive system or an FFS drive system. These display elements are not limited to liquid crystal displays intended for display purposes, and can also be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other purposes, such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.

[0129] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-052144, filed on March 27, 2024, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent comprising the following polymer (A) and component (B): Polymer (A): A polymer 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 a polymer having the following formula (1T ａ As a diamine-derived structural unit, a structural unit (a-1Ta) represented by the following formula (1D ａ The polymer contains a structural unit (a-1Da) represented by the following formula (1): Component (B): Compound (B) represented by the following formula (1): (Formula (1T ａ ) Medium, X ａ represents a tetravalent organic group. Each R independently represents a hydrogen atom or a monovalent organic group. (Formula (1D ａ ) in Y ａ is -Ar-L ０ represents a divalent organic group represented by -Ar'-. Ar and Ar' each independently represent a benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle. Any hydrogen atom on the ring of Ar or Ar' may be substituted with a monovalent group. Each Z independently represents a hydrogen atom or a monovalent organic group. L ０ is a single bond, or -L ａ -A-L ａ’ - represents. ａ , L ａ’ 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). A represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. However, L ａ and L ａ’ represents —O—, A does not have —C(═O)— or —O—C(═O)—.) Component (B): Compound (B) represented by the following formula (1): (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X １ -(Y １ -L) ｎ -Y ２ -X ２ -* (2) (In formula (2), X １ , X ２ are each independently a single bond, —O—, *1-O—CO—*2 (*1 and *2 represent a bond, and *1 is Ar １ or Ar １’ L represents a single bond, -O-, -O-C(=O)- or -C(=O)-O-, and when there are multiple Ls, the multiple Ls may be the same or different from one another, provided that at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y １ , Y ２ each independently represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxy group. １ If there are multiple Y １ may be the same as or different from each other. * represents Ar １ or Ar １’ Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4) and a maleimide group. When formula (1) has a plurality of (q1) to (q4), the plurality of R １ ~R ４ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group, and the monovalent organic group is a carbonyl group, a sulfonyl group, and *1-C(R ｑ１ ) ２ - *2 is bonded to the nitrogen atom via a linking group. ２ represents a hydrogen atom or a monovalent organic group. ｑ１ ) ２ *1 in -*2 represents a bond to the nitrogen atom, and multiple R ｑ１ each independently represents a hydrogen atom or a monovalent organic group. ｑ１ *2 in -*2 bonds to a monovalent organic group having a heteroatom-containing group. ３ represents a hydrogen atom or a monovalent organic group. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a hydrogen atom, a hydroxy group, or a monovalent organic group.

2. The liquid crystal aligning agent according to claim 1, wherein the compound (B) is at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q2-1) to (q2-3), (q3-1) to (q3-3), and (q4-1) to (q4-2):

3. The liquid crystal aligning agent according to claim 1, wherein the content of the compound (B) is 0.1 to 50 parts by mass relative to 100 parts by mass of the polymer (A).

4. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal alignment agent according to any one of claims 1 to 3 to a substrate, baking the substrate, and subjecting the resulting film to an alignment treatment.

5. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 3.

6. A liquid crystal display device comprising the liquid crystal alignment film according to claim 5.

7. The liquid crystal display element according to claim 6, which is of an IPS drive system or an FFS drive system.

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