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

Abstract

The present invention provides a liquid crystal aligning agent which enables the achievement of a liquid crystal alignment film that has a high voltage holding ratio and a high film hardness and is capable of suppressing an AC afterimage.　The liquid crystal aligning agent is characterized by containing the polymer (A) and the component (B) described below.　Polymer (A): A polymer which is selected from the group consisting of a polyimide precursor that has a structural unit derived from a tetracarboxylic acid derivative and a structural unit derived from a diamine, and an imidized polymer that is an imidization 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): A compound (B) which is represented by formula (1). (The meaning of each symbol in formula (1Ta) and formula (1Da) is as defined in the description.) (The meaning of each symbol in formula (CL) is 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] Liquid crystal display elements are required to have high display quality, and one of the required characteristics is, for example, a high voltage holding ratio. For this purpose, Patent Document 1 discloses a composition for a liquid crystal alignment film containing an aromatic diamine such as 1,5-bis(4-aminophenoxy)pentane.

[0004] Japanese Patent Publication No. 06-194670

[0005] Currently, industrially widespread liquid crystal alignment films are produced by rubbing the surface of a film made of a polymer, typically polyamic acid and / or imidized polyimide, formed on an electrode substrate in one direction with a cloth such as cotton, nylon, or polyester. When rubbing to develop alignment characteristics, a problem arises: dust is easily generated due to scraping of the liquid crystal alignment film. This dust can adhere to the surface of the liquid crystal alignment film, potentially resulting in display defects. Furthermore, liquid crystal display devices for mobile applications such as smartphones and in-vehicle applications such as car navigation systems often undergo panel vibration tests as a reliability test. This vibration test is required to eliminate defects such as bright spots. To achieve liquid crystal display devices that do not experience defects associated with rubbing or vibration tests, a liquid crystal alignment film with high film hardness is required. Furthermore, liquid crystal alignment films used in liquid crystal display devices, typically those in the IPS and FFS modes, require high alignment control strength to suppress image retention (hereinafter also referred to as AC image retention) caused by long-term AC drive. In recent years, large-screen, high-definition liquid crystal display elements have become mainstream, and the demand for higher quality liquid crystal display elements has increased more than ever before. As a result of the inventor's investigations, it has been found that conventional techniques cannot provide a liquid crystal alignment film that satisfies these characteristics at a high level.

[0006] The object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film having a high voltage holding ratio, high film hardness, and capable of suppressing AC afterimages to a high level, a liquid crystal alignment film obtained from the liquid crystal alignment 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 Component (B): A 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. ａ ) in Y ａ represents a divalent organic group. Each Z independently represents a hydrogen atom or a monovalent organic group. １１ -L １１ ) ｎ１ -Ak ２ - (L １２ -Ak １２ ) ｎ２ -CL (1) (In formula (1), each CL independently represents a monovalent organic group represented by the following formula (CL): Ak １１ , Ak １２ each independently represents an alkylene group having 1 to 6 carbon atoms; L １１ , L １２ each independently represents —O—C(═O)— or —C(═O)—O—. Ak ２ represents an alkylene group having 4 to 6 carbon atoms. n1 and n2 each independently represent an integer of 1 or 2. １１ , Ak １２ , L １１ , L １２may be the same as or different from each other.) (R １１ , R １２ each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, or an organic group in which —O—, —C(═O)—, —O—C(═O)—, —C(═O)—O—, —C(═O)—NR—, or —NR—C(═O)— is inserted between the carbon-carbon bonds of the hydrocarbon group, and R １１ and R １２ At least one of the groups represents a hydroxyl group-containing group. In addition, R in -C(=O)-NR- or -NR-C(=O)- represents a hydrogen atom or a monovalent organic group. * represents a bond.)

[0008] In this specification, * represents a bond in all cases. Examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Boc represents a tert-butoxycarbonyl group.

[0009] According to the present invention, a liquid crystal aligning agent capable of producing a liquid crystal alignment film having a high voltage holding ratio, high film hardness, and capable of suppressing AC afterimages, the liquid crystal alignment film, and a liquid crystal display device having the liquid crystal alignment film are obtained. The mechanism by which the above-mentioned effects of the present invention are obtained is not entirely clear, but the following is thought to be one of the reasons. First, the high voltage holding ratio and film hardness are obtained by the reaction of multiple functional groups possessed by compound (B) with polymer (A) and crosslinking. In addition, the high reaction efficiency of compound (B) and the ion-trapping effect of the ester bond are thought to contribute to the high voltage holding ratio. Furthermore, compound (B) has high flexibility and plasticity due to the presence of alkylene chains and ester bonds in its structure, which increases the overall stretchability of the alignment film during alignment treatment, resulting in high liquid crystal alignment. This is thought to be the reason for the above-mentioned effects.

[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 ａThe 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 ) X ａExamples of the tetravalent organic group that gives the formula (I) include a tetravalent organic group obtained by removing two acid anhydride groups (-C(=O)-O-C(=O)-) from an aromatic tetracarboxylic acid dianhydride, a tetravalent organic group obtained by removing two acid anhydride groups from an acyclic aliphatic tetracarboxylic acid dianhydride, and a tetravalent organic group obtained by removing two acid 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 aromatic tetracarboxylic acid dianhydride may have a heteroatom in the molecule. 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 is not necessary for the structure to be composed solely of a chain hydrocarbon structure, and it may partly contain an alicyclic structure, an aromatic ring structure, or a heteroatom. Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides 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, the tetracarboxylic acid dianhydride does not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure, an aromatic ring structure, or a heteroatom. Examples of heteroatoms in the tetracarboxylic acid dianhydride include nitrogen atoms, oxygen atoms, sulfur atoms, and silicon atoms. In the tetracarboxylic acid dianhydride, some of the hydrogen atoms in the alicyclic structure, chain hydrocarbon structure, and aromatic ring structure may be substituted with heteroatoms, and the chain structure or cyclic structure may be formed via the heteroatom. From the viewpoint of optimally achieving the effects of the present invention, the aromatic tetracarboxylic acid dianhydride is preferably a tetracarboxylic acid dianhydride having a benzene ring. More preferred X ａThe tetravalent organic group derived from an aromatic tetracarboxylic dianhydride in the above formula is a tetravalent organic group obtained by removing two acid 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',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenyl)-2,4-di ... (phenyloxy)-2,2-diphenylpropanoic dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxydi(1,4-phenylene)bis(phthalic) dianhydride, 4,4'-methylenedi(1,4-phenylene)bis(phthalic) dianhydride, or aromatic tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydrides represented by the following formulas [CA-2] to [CA-8], [CA-11] to [CA-13], [CA-16] to [CA-17], and [CA-19] to [CA-20]. Preferred examples of the acyclic aliphatic tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, or tetracarboxylic acid dianhydrides represented by the following formulae (AL-1) to (AL-7), and tetracarboxylic acid dianhydrides represented by the following formulae [CA-10], [CA-14], [CA-21], and [CA-23] to [CA-25]. Of these, 1,2,3,4-butanetetracarboxylic acid dianhydride is 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 ５ａA 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 ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group. * 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 -21). 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 In the above formula, the monovalent organic group for R 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 ３is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, —SO ２ - or the like, a monovalent group A 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, or 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 obtained by using a diamine compound having two amino groups in the molecule. A preferred specific example of the diamine compound is the diamine "H-N(Z)-Ar-L ０ -Ar'-N(Z)-H" (hereinafter also referred to as specific diamine), or other diamines excluding the specific diamines. Ar and Ar' in the specific diamines each independently represent a benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle. Any hydrogen atom on the rings of Ar and Ar' may be substituted with a monovalent group. Z in the specific diamines each independently represent a hydrogen atom or a monovalent organic group. L in the specific diamines ０ is a single bond, or -L ａ -A-L ａ’ L in the specific diamineａ , L ａ’ are each independently a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-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 -A-L ａ’ A in the formula (1D) represents a divalent organic group having an alkylene structure and having 1 to 10 carbon atoms. ａ A preferred embodiment of Z in the above formula (1T ａ ) are the same as the preferred embodiments of R in

[0021] (Specific Diamine) In the specific diamine, 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 1 to 10 carbon atoms. The -L ａ -A-L ａ’ -L ａ , L ａ’ each independently represents a single bond, —O—, —S—, —C(═O)—, —O—C(═O)—, —C(═O)—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).

[0022] 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.

[0023] Examples of the monovalent group that is a substituent for any hydrogen atom on the rings of Ar and Ar′ of the specific diamine include monovalent groups such as a halogen atom; an alkyl group having 1 to 3 carbon atoms; an alkyl group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with a halogen atom or a hydroxy group; an alkoxy group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms in which at least a portion of the hydrogen atoms is substituted with at least one of the 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.

[0024] 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.

[0025] Above -L ａ -A-L ａ’A in - 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 -A-L ａ’ A in - 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, the monovalent organic group R in the -NR-C(=O)-NR- includes the above L ａ and L ａ’ Examples of the structure include the structures exemplified for R in —C(═O)—NR—, which represents:

[0026] Preferred examples of (p0), (p1), and (p2) are as follows: *-(CH ２ ) ｎ - *, * - (CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ - *, * - (-CH ２ -CH ２ -O) ｎ０ - *, * - (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 -*

[0027] 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.

[0028] *-L ａ -A-L ａ’ -* is preferably in the following form from the viewpoint of suitably obtaining the effects of the present invention. In the formula below, the definitions of m1, m2, n, n', n1, and n2 are the same as in the formula above. n0 is an integer of 1 to 3. Furthermore, in the formula below, R represents a hydrogen atom or a monovalent organic group. When two Rs are present, they each independently have the above definition. As the monovalent organic group, the 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 -CH ２ -O) ｎ０ -* *-O-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２-O-*、 *-C(=O)-(CH ２ ) ｎ -C(=O)-*、 *-C(=O)-NR-(CH ２ ) ｎ -O-*、 *-O-C(=O)-(CH ２ ) ｎ -O-*、 *-O-C(=O)-(CH ２ ) ｎ -O-C(=O)-*、 *-O-C(=O)-(CH ２ ) ｎ -C(=O)-O-*、 *-(CH ２ ) ｍ１ -O-C(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ -* *-O-(CH ２ ) ｍ１ -O-C(=O)-(CH ２ ) ｎ’ -C(=O)-O-(CH ２ ) ｍ２ -O-* *-S-(CH ２ ) ｎ -S-*、 *-C(=O)-NR-(CH ２ ) ｎ -NR-C(=O)-*、 *-C(=O)-O-(CH ２ ) ｎ -O-C(=O)-*、 *-(CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -O-C(=O)-(CH ２ ) ｍ２ -* *-O-(CH ２ ) ｍ１ -C(=O)-O-(CH ２ ) ｎ’ -O-C(=O)-(CH ２ ) ｍ２ -O-* *-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.

[0029] L ０ Specific 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.

[0030] 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 (h1-20). In formulae (h1-1) to (h1-13) and (h1-15) to (h1-20), the bonding positions of the benzene ring are preferably the 1st and 4th positions, and the bonding positions of the naphthalene ring are preferably the 2nd and 6th positions. In formula (h1-4), -CH ２ The total number of - is 10 or less. In formulae (h1-7), (h1-8), (h1-15), and (h1-16), -CH２ The total number of - is 8 or less, and two m's may be the same or different. In addition, the hydrogen atoms on the benzene rings of the following formulas (h1-1) to (h1-13), (h1-15), (h1-16), and (h1-18) to (h1-20) may be substituted with a methyl group, a methoxy group, or a fluorine atom.

[0031] 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;

[0032] 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

[0033] 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)-pi perazine, 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 the following formulae (z-1) to (z-17) and (z-19): heterocycle-containing diamines such as diamines represented by formulas (z-21) to (z-23), or diamines having at least one nitrogen atom-containing structure (excluding the amino group derived from the above-mentioned -N(D)-; hereinafter, also 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 involved in the polycondensation reaction) selected from the group consisting of heterocycles containing nitrogen atoms and secondary or tertiary amino groups, typified by diamines having a diphenylamine structure such as formulas (z-18), (z-22) to (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;

[0034] 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.

[0035] (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-.)

[0036] D in the above-mentioned -N(D)- is preferably a carbamate-based organic group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, a Boc group, etc. A Boc group is particularly preferred from the viewpoints that it is efficiently eliminated by heat, is eliminated at a relatively low temperature, and is discharged as a harmless gas upon elimination.

[0037] 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 Boc.

[0038] 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). In another embodiment, the polymer (A) may contain the structural unit (a-1Da) in an amount of 100 mol % or less, 90 mol % or less, or 80 mol % or less, based on 1 mol of all diamine-derived structural units contained in the polymer (A).

[0039] In one embodiment, the compound of formula (1D ａ ) Y ａ In one embodiment, the polymer (A) preferably contains 1 mol % or more, more preferably 5 mol % or more, of the structural unit (a-1Da), which is a divalent organic group derived from the specific diamine, relative to 1 mol of all structural units derived from the diamine contained in the polymer (A). ａ ) Y ａHowever, the structural unit (a-1Da), which is a divalent organic group derived from the specific diamine, may be 100 mol % or less, 90 mol % or less, or 80 mol % or less, relative to 1 mol of all structural units derived from diamine contained in the polymer (A).

[0040] In one embodiment, the polymer (A) is selected from the group consisting of the above Y ａ 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 above as the other diamine), 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)). From the viewpoint of reducing afterimages due to residual DC, the polymer (A) 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 above as the other diamine), 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. ａ is the specific divalent organic group (b) of the formula (1D ａ The structural unit (a-1Da) 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 (A). Furthermore, the structural unit (a-1Da) may be contained in an amount of 100 mol % or less, or 90 mol % or less, relative to 1 mol of all diamine-derived structural units contained in the polymer (A).

[0041] The liquid crystal aligning agent of the present invention may be composed of two or more types of polymers (A). In one embodiment, the content ratio of one polymer (hereinafter also referred to as polymer (1)) to the other polymer (hereinafter also referred to as polymer (2)) in terms of the mass ratio [polymer (1) / polymer (2)] may be 10 / 90 to 90 / 10, 20 / 80 to 90 / 10, or 20 / 80 to 80 / 20.

[0042] <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.

[0043] 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.

[0044] 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.

[0045] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, maleic 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; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; Examples of the amino acid include 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, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate.

[0046] 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.

[0047] 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.

[0048] <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. When the molecular weight is in this range, good alignment and stability of the liquid crystal display device can be ensured.

[0049] 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 a polymer selected from the group consisting of polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate. 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).

[0050] <Component (B)> The liquid crystal aligning agent of the present invention contains a compound (B) represented by the following formula (1): CL-(Ak １１ -L １１ ) ｎ１ -Ak ２ - (L １２ -Ak １２ ) ｎ２ -CL (1) (In formula (1), each CL independently represents a monovalent organic group represented by the following formula (CL): Ak １１ , Ak １２each independently represents an alkylene group having 1 to 6 carbon atoms; L １１ , L １２ each independently represents —O—C(═O)— or —C(═O)—O—. Ak ２ represents an alkylene group having 4 to 6 carbon atoms. n1 and n2 each independently represent an integer of 1 or 2. １１ , Ak １２ , L １１ , L １２ may be the same as or different from each other.) (R １１ , R １２ each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, or an organic group in which —O—, —C(═O)—, —O—C(═O)—, —C(═O)—O—, —C(═O)—NR—, or —NR—C(═O)— is inserted between the carbon-carbon bonds of the hydrocarbon group, and R １１ and R １２ At least one of the groups represents a hydroxy group-containing group. In addition, R in -C(=O)-NR- or -NR-C(=O)- represents a hydrogen atom or a monovalent organic group. * represents a bond.) Examples of the substituent of the hydrocarbon group include a hydroxy group and a halogen atom. Examples of the monovalent organic group for R in -C(=O)-NR- or -NR-C(=O)- include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, an alkylsilyl group having 1 to 4 carbon atoms, an alkoxysilyl group having 1 to 4 carbon atoms, or a monovalent organic group in which at least a portion of the hydrogen atoms of these groups have been substituted with at least one of a halogen atom and a hydroxy group.

[0051] Examples of the substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms include a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 4 carbon atoms, and a substituted or unsubstituted alkynyl group having 2 to 4 carbon atoms. Examples of the substituent on the hydrocarbon group include a hydroxy group and a halogen atom.

[0052] -(Ak １１-L １１ ) ｎ１ -Ak ２ - (L １２ -Ak １２ ) ｎ２ Preferred examples of - include the following structures: -(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 -; -(CH ２ ) ｎ１ -OC(=O)-(CH ２ ) ｎ３ -C(=O)-O-(CH ２ ) ｎ５ -; -(CH ２ ) ｎ１ -C(=O)-O-(CH ２ ) ｎ３ -OC(=O)-(CH ２ ) ｎ５ The above n1 to n2 and n4 to n5 are each independently an integer of 1 to 6. n3 is an integer of 4 to 6, and more preferably an integer of 4 or 6. From the viewpoint of suitably obtaining the effects of the present invention, n1, n2, n4, and n5 are more preferably integers of 2 to 6.

[0053] The compound (B) is preferably at least one compound selected from the group consisting of the following formulae (b-1) to (b-4):

[0054] 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).

[0055] <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.

[0056] 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-diethylacetamide, 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, 3-butoxy-N,N-dimethyl Examples of suitable solvents include 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, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-diethylacetamide, 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.

[0057] 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 to these.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the solvent (hereinafter also referred to as additive components). Examples of such additive components include a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compound, 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 the 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.

[0062] 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;

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] (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)).

[0068] <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.

[0069] 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.

[0070] <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 hot air 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.

[0071] <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.

[0072] 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.

[0073] (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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] The liquid crystal composition is not particularly limited and is a composition containing at least one liquid crystal compound (liquid crystal molecule). It may be a liquid crystal composition having a positive dielectric anisotropy (also called a positive liquid crystal composition or positive liquid crystal) or a liquid crystal composition having a negative dielectric anisotropy (also called a negative liquid crystal composition or negative liquid crystal). However, a negative liquid crystal material is preferred. The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring. It may also contain a compound having two or more rigid moieties (mesogenic skeletons) exhibiting liquid crystallinity within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl or terphenyl structures are connected by an alkyl group). The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase. Furthermore, additives may be further added to the liquid crystal composition in order to improve the liquid crystal alignment properties. Examples of such additives include photopolymerizable monomers such as compounds having a polymerizable group, optically active compounds (e.g., S-811 manufactured by Merck & Co., Inc.), antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, or polymerization inhibitors. Examples of positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck & Co., Inc. Examples of negative liquid crystals include MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, and MLC-7029 manufactured by Merck Co., Ltd.; and NA-1559 manufactured by DIC Corporation. For PSA mode, an example of a liquid crystal containing a compound having a polymerizable group is MLC-3023 manufactured by Merck Co., Ltd. Next, polarizing plates are installed. 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.

[0078] 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 physical properties are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve DMF: N,N-dimethylformamide (Tetracarboxylic acid dianhydrides) CA-1 to CA-5: Compounds represented by the following formulas (CA-1) to (CA-5), respectively (Diamine) DA-1 to DA-5: Compounds represented by the following formulas (DA-1) to (DA-5), respectively (Additives) AD-1 to AD-4: Compounds represented by the following formulas (AD-1) to (AD-4), respectively Among the above additives, AD-4 is included in the range of the specific additive corresponding to compound (B) of the present application.

[0079] <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).

[0080] <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 Resonac Corporation), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonac Corporation) 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).

[0081] [Synthesis of Additive] AD-4 is a novel compound not disclosed in the literature, and the product in Additive 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)

[0082] Additive Synthesis Example 1: Synthesis of AD-4 Under a nitrogen atmosphere, 4,4'-(butane-1,4-diylbis(oxy))bis(4-oxobutanoic acid) (5.2 g, 18 mmol), methylene chloride (DCM, 42 g), and DMF (0.1 g) were added to a 300 mL four-neck flask and stirred while cooling on ice. Oxalyl chloride (5.7 g, 45 mmol) was added thereto, and the mixture was stirred while returning to room temperature. After the generation of bubbles ceased, the mixture was concentrated using an evaporator, and methylene chloride (20 g) was added to obtain solution (A). O-trimethylsilyl-N-(2-trimethylsilyloxyethyl)ethanolamine, methylene chloride (20 g), and triethylamine (TEA, 4.6 g, 45 mmol) were added to another 300 mL four-neck flask and stirred while cooling on ice. Solution (A) was slowly added thereto, and the mixture was returned to room temperature and stirred. After the reaction was completed, the precipitate was removed by filtration, and the solution was concentrated using an evaporator. Ethyl acetate (250 g) and purified water (75 g) were added for separation and washing. The resulting organic layer was concentrated to obtain AD-4-1 (13.3 g, 17.7 mmol, yield 98.4%, light brown oil).１ H-NMR (500MHz, DMSO-d ６ ): δ (ppm) = 4.02-3.97 (m, 4H), 3.67-3.30 (m, 16H), 2.63-2.46 (m, 8H), 1.61-1.58 (m, 4H), 0.06 (s, 36H) Under a nitrogen atmosphere, AD-4-1 (13.3 g, 17.7 mmol), ethanol (EtOH, 65 g), and acetic acid (AcOH, 4.2 g, 70.8 mmol) were added to a 300 mL four-neck flask and stirred at 80° C. After completion of the reaction, the mixture was concentrated using an evaporator to obtain AD-4 (8.3 g, 17.7 mmol, yield 100%, reddish-brown oil). １ H-NMR (500MHz, DMSO-d ６ ): δ (ppm) = 5.21-4.30 (m, 4H), 3.97-3.92 (m, 4H), 3.48-3.24 (m, 16H), 2.58-2.55 (m, 4H), 2.44-2.40 (m, 4H), 1.56-1.53 ​​(m, 4H)

[0083] [Synthesis of Polymer] <Synthesis Example 1> DA-1 (1.43 g, 5.00 mmol), DA-2 (0.733 g, 3.00 mmol), DA-4 (0.793 g, 2.00 mmol), and NMP (26.6 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature (25°C) while supplying nitrogen to dissolve the mixture. Thereafter, CA-4 (2.09 g, 9.60 mmol) and NMP (10.4 g) were added, and the mixture was stirred at 50°C for 18 hours to obtain a solution of polyamic acid (A-1) with a solids concentration of 12 mass% (viscosity: 450 mPa s).

[0084] Synthesis Example 2 DA-3 (2.550 g, 8.00 mmol), DA-5 (0.634 g, 2.00 mmol), and NMP (28.7 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 (25 ° C.) while supplying nitrogen. Thereafter, CA-2 (3.003 g, 7.50 mmol) and NMP (6.4 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature (25 ° C.), and CA-5 (0.690 g, 2.20 mmol) and NMP (3.9 g) were added, and the mixture was stirred at room temperature (25 ° C.) for 18 hours to obtain a solution of polyamic acid (A-2) with a solids concentration of 15% by mass (viscosity: 530 mPa s).

[0085] Synthesis Example 3 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, yielding a solution of polyamic acid (A-3) 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.

[0086] Synthesis Example 4 DA-2 (0.977 g, 4.00 mmol), DA-3 (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-4) 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.

[0087] The types and amounts of the tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 4 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.

[0088]

[0089] [Preparation of Liquid Crystal Alignment Agent] <Example 1> To the solution (2.80 g) of the polyamic acid (A-1) obtained in Synthesis Example 1, the solution (5.23 g) of the polyamic acid (A-2) obtained in Synthesis Example 2, NMP (5.37 g), BCS (5.00 g), AD-1 (1 mass% GBL solution, 1.12 g), and AD-4 (10 mass% NMP solution, 0.49 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.

[0090] <Example 2 and Comparative Examples 1 to 4> By carrying out the same operation as in above-mentioned Example 1, except that the type and amount of polymer solution, solvent and additive used are changed as shown in Table 2, obtain the liquid crystal aligning agent (AL-2) of Example 2 of the present invention and the liquid crystal aligning agent (AL-C1) to (AL-C4) of Comparative Examples 1 to 4.

[0091]

[0092] In Table 2, the mass ratios of polymer 1, polymer 2, additive 1, specific additive, and other additives represent the proportions (parts by mass) of each polymer solid content and additive 1 relative to 100 parts by mass of the total of the polymer components. In Table 2, the blending moles of the specific additive and other additives represent the number of moles of each additive compound contained in 20.0 g of each liquid crystal alignment agent.

[0093] [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 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 Corporation). Subsequently, the substrate was washed by ultrasonic irradiation in pure water for 1 minute, water droplets were removed by air blowing, and then dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film (hereinafter, the alignment treatment after the coating film formation is also referred to as a rubbing alignment treatment). Two substrates with this liquid crystal alignment film were prepared, and spherical spacers with a particle size of 4 μm were sprayed on the liquid crystal alignment film surface of one of them. 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 it with the rubbing direction reversed and the film surfaces facing each other. Subsequently, a heat treatment was performed 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.

[0094] <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.

[0095] 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 4 μm-high columnar spacers and an ITO film formed on the backside. The resulting substrate was dried on a hot plate at 80°C for 2 minutes and then baked in a hot air circulating oven at 230°C for 20 minutes to form a coating film with a thickness of 60 nm. The coating film was then subjected to the rubbing alignment treatment described above to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was aligned so that the direction dividing the interior angle of the pixel bends was parallel to the alignment direction of the liquid crystal. The liquid crystal alignment film formed on the counter substrate was aligned 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 set, and a sealant (Mitsui Chemicals XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the other substrate, with the alignment directions of the liquid crystal alignment films facing each other at 0°. The attached substrates were then pressed together and heated in a hot air circulating oven at 150°C for 60 minutes to cure the sealant, producing an empty cell. Negative liquid crystal NA-1559 (DIC) was injected into this empty cell by a reduced pressure 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.

[0096] [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.

[0097] <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.

[0098] <Evaluation of Alignment Stability by Long-Term AC Drive> This evaluation is to evaluate the afterimage (also called AC afterimage) that occurs due to the deterioration of the alignment performance of the liquid crystal alignment film during long-term AC drive. Using the FFS drive liquid crystal cell prepared above, a high-brightness backlight (light source: LED, brightness: 30,000 cd / m) with a surface temperature of 50°C was used. ２ ) and an AC voltage of ±6.5 V at a frequency of 30 Hz was applied for 120 hours. The pixel electrode and common electrode of the liquid crystal cell were then shorted and left at room temperature (23°C) for one day. After leaving the liquid crystal cell, it was placed between two polarizing plates arranged so that their polarization axes were perpendicular to each other. The backlight was turned on with no voltage applied, and the liquid crystal cell was adjusted to minimize the transmitted light intensity of the first region of the first pixel. The rotation angle Δ required to rotate the liquid crystal cell to minimize the transmitted light intensity of the second region of the first pixel was then calculated. The first and second regions of the second pixel were similarly compared, and the same angle Δ was calculated. The average of the angles Δ for the first and second pixels was then calculated as the rotation angle Δ of the liquid crystal cell. It can be said that the smaller the rotation angle Δ, the better the stability of the liquid crystal alignment.

[0099] [Evaluation of Film Hardness] The liquid crystal alignment agent obtained above was applied to an ITO substrate by spin coating. After drying for 2 minutes on a hot plate at 80°C, it was baked for 20 minutes in a hot air circulation oven at 230°C to obtain a substrate with a liquid crystal alignment film with a thickness of 60 nm. This liquid crystal alignment film was then subjected to a rubbing alignment treatment twice with a rayon cloth (HY-5318, manufactured by Hyperflex Corporation) (roller diameter: 120 mm, roller rotation speed: 1000 rpm, movement speed: 20 mm / sec, indentation length: 0.5 mm), and the haze value (turbidity) of the film was evaluated using a haze meter (HZ-V3, manufactured by Suga Test Instruments Co., Ltd.). The smaller the haze value, the less the film was scraped, i.e., the higher the film hardness.

[0100] The evaluation results of the voltage holding ratio, alignment stability, and film hardness using each of the liquid crystal alignment agents of Examples 1 and 2 and Comparative Examples 1 to 4 are shown in Table 3. The numbers in parentheses for the polymer component, additive 1, specific additive, and other additives represent the proportion (parts by mass) of each polymer solid content and additive 1 when the total content of the polymer solid content is 100 parts by mass. In Table 3, the blending molar amount of the specific additive and other additives represents the number of moles (μmol) of each additive compound contained in 20.0 g of each liquid crystal alignment agent.

[0101]

[0102] As shown in Table 3, the liquid crystal alignment film obtained from the liquid crystal aligning agent of Example 1 to which the specific additive was added had better voltage holding ratio, alignment stability, and film hardness than the liquid crystal alignment film obtained from the liquid crystal aligning agent of Comparative Example 1 to which the specific additive was not added. Furthermore, the liquid crystal alignment films obtained from the liquid crystal aligning agents of Examples 1 and 2 to which the specific additive was added had better alignment stability than the liquid crystal alignment films obtained from the liquid crystal aligning agents of Comparative Examples 2 and 3 to which another additive (AD-2) was added. Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of Example 2 to which the specific additive was added had a better voltage holding ratio than the liquid crystal alignment film obtained from the liquid crystal aligning agent of Comparative Example 4 to which another additive (AD-3) was added.

[0103] 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.

[0104] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-092492 filed on June 6, 2024 are hereby incorporated by reference as the disclosure of the present invention.

Claims

1. A liquid crystal aligning agent characterized by containing 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 Component (B): A 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. ａ ) in Y ａ represents a divalent organic group. Each Z independently represents a hydrogen atom or a monovalent organic group. １１ -L １１ ) ｎ１ -Ak ２ - (L １２ -Ak １２ ) ｎ２ -CL (1) (In formula (1), each CL independently represents a monovalent organic group represented by the following formula (CL): Ak １１ , Ak １２ each independently represents an alkylene group having 1 to 6 carbon atoms; L １１ , L １２ each independently represents —O—C(═O)— or —C(═O)—O—. Ak ２ represents an alkylene group having 4 to 6 carbon atoms. n1 and n2 each independently represent an integer of 1 or 2. １１ , Ak １２ , L １１ , L １２ may be the same as or different from each other.) (R １１ , R １２ each independently represents a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 4 carbon atoms, or an organic group in which —O—, —C(═O)—, —O—C(═O)—, —C(═O)—O—, —C(═O)—NR—, or —NR—C(═O)— is inserted between the carbon-carbon bonds of the hydrocarbon group, and R １１ and R １２ At least one of the groups represents a hydroxyl group-containing group. In addition, R in -C(=O)-NR- or -NR-C(=O)- represents a hydrogen atom or a monovalent organic group. * represents a bond.) 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 (b-1) to (b-4):

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 aligning agent according to any one of claims 1 to 3 to a substrate, baking the applied film, and then 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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