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

Abstract

The present application provides a liquid crystal alignment agent which is excellent in printability, and which can provide a liquid crystal alignment film having a high voltage retention rate and a small accumulated charge amount, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film. A liquid crystal alignment agent characterized by containing the following polymer (A) and (B) components. 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, and, as the structural unit derived from a tetracarboxylic acid derivative, contains a structural unit (a-1Ta) represented by the following formula (1T a ); and, as the structural unit derived from a diamine, contains a structural unit (a-1Da) represented by the following formula (1D a ). (B) component: a compound (B) represented by the following formula (1). (The meanings of the symbols in the above formula (1T a ) are as defined in the description. ) (The meanings of the symbols in the above formula (1D a ) are as defined in the description. ) (B) component: a compound (B) represented by the following formula (1). ( The meanings of the symbols in the above formula (1) are as defined in the description. )

Description

Technical Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film. Background Technology

[0002] Liquid crystal display (LCD) elements are widely used in applications ranging from small devices like mobile phones and smartphones to larger applications such as televisions and monitors. Furthermore, various driving methods have been developed, including different electrode structures and the physical properties of the liquid crystal molecules used. Examples of known LCD elements using various modes include TN (Twisted Nematic), STN (Super Twisted Nematic), VA (Vertical Alignment), IPS (In-Plane Switching), and FFS (Fringe Field Switching). These LCD elements typically have a liquid crystal alignment film, essential for controlling the alignment of the liquid crystal molecules. Polyamic acid and its derivatives (such as polyimide) are commonly used as materials for the liquid crystal alignment film (see Patent Document 1).

[0003] Existing technical documents Patent documents Patent Document 1: WO2022 / 220199 Summary of the Invention

[0004] The problem that the invention aims to solve Liquid crystal display elements typically include: a liquid crystal layer sandwiched between an element substrate and a color filter substrate; pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer; a liquid crystal alignment film that controls the orientation of the liquid crystal molecules in the liquid crystal layer; and a thin film transistor (TFT) that converts the electrical signals supplied to the pixel electrodes; etc.

[0005] In recent years, large-screen and high-definition liquid crystal display elements have become mainstream, leading to the development of specifications for display elements with increased pixel counts, such as 4K and 8K. The liquid crystal alignment film requires characteristics that ensure uniform film thickness even with surface variations on substrates containing TFTs, and demands liquid crystal alignment agents with superior printability compared to previous methods.

[0006] Furthermore, external stimuli such as light and heat can sometimes cause image burn-in (image burn-in of zones and lines), unevenness, or contamination over time, resulting in display defects. To suppress these display defects, liquid crystal alignment films with excellent high voltage retention are required, and this high voltage retention becomes a condition for achieving long-term reliability in so-called display quality.

[0007] Furthermore, in liquid crystal display elements such as IPS and FFS types, static electricity tends to accumulate within the liquid crystal cell. Sometimes, the application of asymmetrical voltage generated by the drive can also cause charge accumulation. This leads to the following problems: these accumulated charges can disrupt the alignment of the liquid crystal or affect the display in the form of image retention, significantly degrading the display quality of the liquid crystal display element. Therefore, the liquid crystal alignment film requires a low amount of accumulated charge.

[0008] In view of the above, the object of the present invention is to provide a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film, wherein the liquid crystal alignment agent has excellent printability and can produce a liquid crystal alignment film with high voltage retention rate. Furthermore, the object of the present invention is also to provide a liquid crystal alignment agent capable of producing a liquid crystal alignment film with low charge accumulation, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

[0009] Solution for solving the problem In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved by using a specific compound, thereby completing the present invention.

[0010] The present invention is characterized by a liquid crystal alignment agent containing polymers (A) and (B) thereof; a liquid crystal alignment film obtained from the liquid crystal alignment agent; or a liquid crystal display element having the liquid crystal alignment film.

[0011] Polymer (A): A polymer selected from the group consisting of a polyimide precursor having structural units derived from a tetracarboxylic acid derivative and structural units derived from a diamine, and an imidized polymer of an imidized product of the polyimide precursor, wherein the structural unit derived from the tetracarboxylic acid derivative comprises the following formula (1T) a The structural unit (a-1Ta) shown in the figure, as a structural unit derived from diamine, contains the following formula (1D). a The structural unit (a-1Da) is shown in the figure.

[0012] (B) Component: Compound (B) as shown in formula (1) below. (Formula (1T)) a In ), X a The symbol indicates a tetravalent organic group. Each R independently represents a hydrogen atom or a monovalent organic group. (Formula (1D)) a ), Y aThe symbols -Ar-L0-Ar'- represent divalent organic groups. Ar and Ar' each independently represent a benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle. Any hydrogen atom on the ring of Ar or Ar' may optionally be replaced by a monovalent group. Z each independently represents a hydrogen atom or a monovalent organic group. L0 represents a single bond or -L a -A-L a’ -. L a L a’ Each can independently represent a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR- (where R represents a hydrogen atom or a monovalent organic group), or -NR-C(=O)- (where R represents a hydrogen atom or a monovalent organic group). A represents a divalent organic group with 1 to 10 carbon atoms having an alkylene structure. Among these, in L... a and L a’ In the case of -O-, A does not have -C (=O)- or -O-C (=O)-. (In equation (1), Ar1 and Ar) 1’ Each of the following independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, wherein one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring are optionally substituted by a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2).

[0013] *-X1-(Y1-L) n -Y2-X2-* (2) (In equation (2), X1 and X2 independently represent single bonds, -O-, *1-O-CO-*2 (*1 and *2 represent bonded bonds, *1 and Ar1 or Ar) 1’ (Bonding). L represents a single bond, -O-, -O-C(=O)-, or -C(=O)-O-. In the presence of multiple Ls, the Ls may optionally be the same or different from each other. At least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer from 1 to 6. Y1 and Y2 each independently represent a divalent hydrocarbon group with 1 to 6 carbon atoms, wherein a portion of the hydrogen atoms in the divalent hydrocarbon group may optionally be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group. In the presence of multiple Y1s, the multiple Y1s may optionally be the same or different from each other. Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4) and maleimide group. It should be noted that when there are multiple (q1) to (q4) in formula (1), the multiple R1 to R4 may optionally be the same or different from each other. (In formula (q1), R1 represents a monovalent organic group, which is derived from a carbonyl group, a sulfonyl group, and *1-C(R) group.) q1 Any linking group in )2-*2 is bonded to a nitrogen atom. R2 represents a hydrogen atom or a monovalent organic group. *1-C(R q1 In )2-*2, *1 represents the bond with the nitrogen atom, R q1 Represents a hydrogen atom or a monovalent organic group. *1-C(R) q1 In formula (q2), *2 is bonded to a monovalent organic group containing a heteroatom. In formula (q2), R3 represents a hydrogen atom or a monovalent organic group. In formula (q3), R4 represents a hydrogen atom, a hydroxyl group, a halogen atom, or a monovalent organic group. In formula (q4), R5 represents a hydrogen atom, a hydroxyl group, or a monovalent organic group. It should be noted that in this specification, * denotes a bond in all cases. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0014] Invention Effects According to the present invention, a liquid crystal alignment agent with excellent printability and capable of producing a liquid crystal alignment film exhibiting high voltage retention, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film can be obtained. Furthermore, a liquid crystal alignment agent capable of producing a liquid crystal alignment film with low accumulated charge, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film can be obtained.

[0015] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but the following content can be considered as one of the reasons.

[0016] First, compound (B) can be considered to possess high flexibility and plasticity due to the presence of alkylene chains and ester bonds in its structure. Furthermore, due to its relatively small molecular weight, molecular movement within the film is smooth during the drying process, easily resulting in a smooth coating. Additionally, by having compound (B) present near polymer (A) or being introduced into the structure of polymer (A), the ester bonds in compound (B) interact with ionic impurities that contribute to poor performance, thereby increasing the voltage retention rate by suppressing impurity diffusion and trapping the impurities. Moreover, the presence of compound (B) near polymer (A) or its introduction into the structure of polymer (A), being a compound with a relatively small molecular weight, can lead to a dense coating, increasing the overall resistivity of the film and thus reducing the amount of accumulated charge. Detailed Implementation

[0017] <Polymer (A)> The polyimide precursor in the polymer (A) of the present invention has the above formula (1T) aThe structural unit (a-1Ta) shown is a structural unit derived from a tetracarboxylic acid derivative. It should be noted that the polymer (A) can be composed of one or more types, and the structural unit (a-1Ta) can also be one or more types.

[0018] (The structural units of polymer (A) derived from tetracarboxylic acid derivatives) The polyimide precursor in the polymer (A) of the present invention has the above formula (1T) a The structural unit (a-1Ta) shown is a structural unit derived from a tetracarboxylic acid derivative.

[0019] As provided by the above formula (1T) b X a The tetravalent organic groups can be listed as follows: tetravalent organic groups obtained by removing two anhydride groups (-C(=O)-O-C(=O)-) from aromatic tetracarboxylic dianhydrides, tetravalent organic groups obtained by removing two anhydride groups from acyclic aliphatic tetracarboxylic dianhydrides, or tetravalent organic groups obtained by removing two anhydride groups from alicyclic tetracarboxylic dianhydrides.

[0020] Here, the aromatic tetracarboxylic dianhydride is obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the aromatic ring.

[0021] Acyclic aliphatic tetracarboxylic dianhydrides are obtained by intramolecular dehydration of the four carboxyl groups bonded to a chain hydrocarbon structure. It is not necessary for the structure to consist solely of a chain hydrocarbon; a portion of the structure may also possess an alicyclic or aromatic ring structure.

[0022] Alicyclic tetracarboxylic dianhydrides are acidic dianhydrides obtained through intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. None of these four carboxyl groups are bonded to an aromatic ring. Furthermore, it is not necessary for the structure to consist solely of an alicyclic structure; it can also have a chain hydrocarbon structure or an aromatic ring structure in a portion thereof.

[0023] From the viewpoint of adequately achieving the effects of the present invention, the above-mentioned aromatic tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride having a benzene ring. More preferably, X a The tetravalent organic group derived from the aromatic tetracarboxylic acid dianhydride is a tetravalent organic group obtained by removing two anhydride groups from the following aromatic tetracarboxylic acid dianhydrides.

[0024] Pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-perfluoroisopropylidene di(phthalic anhydride), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'-biphenyl Aromatic tetracarboxylic acid dianhydrides include tetracarboxylic acid dianhydrides such as 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol dihydrotriphenyl ester, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-oxobis(1,4-phenylene)bis(phthalic acid) dianhydride, or 4,4'-methylenebis(1,4-phenylene)bis(phthalic acid) dianhydride.

[0025] As preferred examples of the above-mentioned acyclic aliphatic tetracarboxylic dianhydrides, examples include 1,2,3,4-butanetetracarboxylic dianhydrides, or tetracarboxylic dianhydrides represented by formulas (AL-1) to (AL-7) below, with 1,2,3,4-butanetetracarboxylic dianhydrides being the most preferred. The aforementioned alicyclic tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride having a cyclobutane ring structure, or a tetravalent organic group having an alicyclic structure containing five or more members (T). 5a Tetracarboxylic acid dianhydride.

[0026] As a preferred specific example of a tetracarboxylic dianhydride having a cyclobutane ring structure, a tetracarboxylic dianhydride having a tetravalent organic group as shown in the following formula (x-1) can be cited. (In formula (x-1), R1 to R4 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organic group containing a fluorine atom with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, an alkoxyalkyl group with 2 to 6 carbon atoms, an alkoxycarbonyl group with 2 to 6 carbon atoms, or a phenyl group. * indicates a bond.)

[0027] Specific examples of alkyl groups in formula (x-1) where R1 to R4 have 1 to 6 carbon atoms, preferably 1 to 4, include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl. Specific examples of alkenyl groups in formula (x-1) where R1 to R4 have 2 to 6 carbon atoms, preferably 2 to 4, include vinyl, propenyl, and butenyl, which can be linear or branched. Specific examples of alkynyl groups in formula (x-1) where R1 to R4 have 2 to 6 carbon atoms, preferably 2 to 4, include ethynyl, 1-propynyl, and 2-propynyl.

[0028] Examples of monovalent organic groups containing fluorine atoms in R1 to R4, with 1 to 6 carbon atoms (preferably 1 to 4), include fluoromethyl, trifluoromethyl, trifluoromethoxy, 2,2,2-trifluoroethyl, 2,2,2-trifluoroethoxy, pentafluoroethyl, and pentafluoropropyl.

[0029] Wherein, the above formula (x-1) is preferably a group selected from the group consisting of the following formulas (x1-1) to (x1-6). As the aforementioned tetravalent organic group (T) 5a Preferably, the alicyclic organic group has a five- to eight-membered ring structure and is tetravalent; more preferably, it has a five- to seven-membered ring structure and is tetravalent. It should be noted that an alicyclic structure with five or more members refers to a polycyclic structure in which each ring contains five or more atoms. Furthermore, the alicyclic structure only needs to be bonded to at least one of the two anhydride groups, and can also have a chain hydrocarbon structure or an aromatic ring structure along with the alicyclic structure.

[0030] As the aforementioned tetravalent organic group (T) 5a A preferred specific example of ) can be listed as the following formula (X) 5a -1) ~ (X) 5a -18) represents a tetravalent organic group. From the viewpoint of properly obtaining the effects of the present invention, the tetravalent organic group (T 5a (X) is more preferably (X) 5a -1) ~ (X) 5a -4). From the viewpoint of properly obtaining the effects of the present invention, the structural unit (a-1Ta) of 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 mole of all structural units derived from tetracarboxylic acid derivatives of the polyimide precursor.

[0031] Furthermore, the structural unit (a-1Ta) of the polyimide precursor in the polymer (A) of the present invention can be 100 mol% or less, 95 mol% or less, or 90 mol% or less, relative to all structural units derived from tetracarboxylic acid derivatives of the polyimide precursor.

[0032] As in the above formula (1T) a The R monovalent organic group in ) can be listed as: monovalent hydrocarbon groups with 1 to 6 carbon atoms; the methylene group of this hydrocarbon group is represented by -O-, -S-, -CO-, -COO-, -COS-, -NR-. 3 -、-CO-NR 3 -, -Si(R) 3 )2-(where R 3 A monovalent group A formed by replacing hydrogen atoms or monovalent hydrocarbon groups with 1 to 6 carbon atoms, such as -SO2-; a monovalent group formed by replacing at least one of the hydrogen atoms bonded to carbon atoms of the above-mentioned monovalent hydrocarbon group or monovalent group A with halogen atoms, hydroxyl, alkoxy, nitro, amino, mercapto, nitroso, alkylsilyl, alkoxysilyl, silanol, sulfinyl, phosphin, carboxyl, cyano, sulfonyl, acyl, etc.; a monovalent group having a heterocyclic ring.

[0033] As the above formula (1T) a R in the form of a monovalent organic group is preferably an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, or a tert-butoxycarbonyl group, more preferably an alkyl group with 1 to 3 carbon atoms, and even more preferably a methyl group.

[0034] From the viewpoint of properly obtaining the effects of the present invention, the above formula (1T) a In the ), each of the two Rs is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0035] The polyimide precursor in the polymer (A) of the present invention comprises the above formula (1D) a The structural unit (a-1Da) shown above is a structural unit derived from diamine. a The structural unit (a-1Da) shown can be obtained, for example, by using the diamine "H-N(Z)-Ar-L0-Ar'-N(Z)-H" (hereinafter also referred to as "specific diamine").

[0036] The above formula (1D) a The preferred method of Z in (1T) is the same as the above formula (1T). a The preferred method for R in ) is the same.

[0037] The above formula (1D) a ) Y aIn Ar and Ar', each independently represents 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 optionally substituted with a monovalent group. A represents a divalent organic group with 1 to 10 carbon atoms having an alkylene structure.

[0038] The above formula (1D) a L a L a’ Each can be independently represented as a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR- (where R represents a hydrogen atom or a monovalent organic group), or -NR-C(=O)- (where R represents a hydrogen atom or a monovalent organic group).

[0039] As a representation of L a L a’ The monovalent organic group R in -C(=O)-NR- or -NR-C(=O)- can be exemplified as: alkyl with 1 to 3 carbon atoms, alkoxy with 1 to 3 carbon atoms, alkenyl with 2 to 3 carbon atoms, acyl with 2 to 3 carbon atoms, alkylsilyl with 1 to 3 carbon atoms, alkoxysilyl with 1 to 3 carbon atoms, or a monovalent organic group in which at least a portion of the hydrogen atoms of these groups are replaced by at least one of a halogen atom and a hydroxyl group.

[0040] As the above equation (1D) a Substituents on any hydrogen atom of the Ar and Ar' rings of Ar are monovalent groups, which can be listed as: halogen atoms; alkyl groups with 1 to 3 carbon atoms; alkyl groups with 1 to 3 carbon atoms in which at least part of the hydrogen atoms are replaced by halogen atoms or hydroxyl groups; alkoxy groups with 1 to 3 carbon atoms; alkoxy groups with 1 to 3 carbon atoms in which at least part of the hydrogen atoms are replaced by at least one of the above-mentioned halogen atoms and hydroxyl groups; alkenyl groups with 2 to 3 carbon atoms; acyl groups with 2 to 3 carbon atoms; alkylsilyl groups with 1 to 3 carbon atoms; alkoxysilyl groups with 1 to 3 carbon atoms; and monovalent groups such as hydroxyl and nitrile groups.

[0041] Specific examples of Ar and Ar' mentioned above 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-tert-butyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, and 2-butoxy-1,4-phenylene. Phenylidene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, etc., can have substituted benzene rings; 4,4'-biphenylene, 2-methyl-4,4'-biphenylene, 2-ethyl-4,4'-biphenylene, 2-propyl-4,4'-biphenylene, 2-butyl-4,4'-biphenylene 2-tert-butyl-4,4'-biphenylene, 2-methoxy-4,4'-biphenylene, 2-ethoxy-4,4'-biphenylene, 2-fluoro-4,4'-biphenylene, 3-methyl-4,4'-biphenylene, 3-ethyl-4,4'-biphenylene, 3-propyl-4,4'-biphenylene, 3-butyl-4,4'-biphenylene, 3-tert-butyl-4,4'-biphenylene, 3-methoxy-4,4'-biphenylene, 3-ethoxy-4,4'-biphenylene Biphenyl structures with substituents, such as 3-fluoro-4,4'-biphenylene, 2,2'-dimethyl-4,4'-biphenylene, 3,3'-dimethyl-4,4'-biphenylene, 3,3'-biphenylene, 5-methyl-3,3'-biphenylene, and 5,5'-dimethyl-3,3'-biphenylene; naphthalene rings with substituents, such as 1,5-naphthylene, 2,6-naphthylene, and 1-methyl-2,6-naphthylene; or the following structures (Ht-1) to (Ht-3). The above formula (1D) a In the alkylene group, A is a divalent organic group with 1 to 10 carbon atoms having an alkylene structure. When the alkylene structure has three or more carbon-carbon bonds, any carbon-carbon bond constituting the alkylene structure may be optionally replaced by a carbon-carbon double bond.

[0042] A is preferably an alkylene group having 1 to 10 carbon atoms (p0); a divalent organic group formed by inserting -O-, -C(=O)-, -NH-, -O-C(=O)-, or -C(=O)-O- between the carbon-carbon bonds of the alkylene group (p1); or a divalent organic group 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 (p2).

[0043] Here, as the R monovalent organic group in the above-mentioned -NR-C(=O)-NR-, examples can be listed for those representing L. a and L a’ The structure exemplified by R in -C(=O)-NR-.

[0044] Preferred specific examples of (p0), (p1), and (p2) are shown below.

[0045] *-(CH2) n -*; *-(CH2) n1 -O-(CH2) n2 -*; *-(CH2) m1 -O-C(=O)-(CH2) n’ -C(=O)-O-(CH2) m2 -*; *-(CH2) m1 -C(=O)-O-(CH2) n’ -O-C(=O)-(CH2) m2 -*; *-(CH2) n1 -NR-C (=O) -NR- (CH2) n2 -*.

[0046] In the above chemical formula, R represents a hydrogen atom or a monovalent organic group. Examples of such monovalent organic groups that represent L include those shown above. a and L a’ The structure is illustrated by R in -C(=O)-NR-. The two Rs may optionally be the same as or different from each other.

[0047] n is an integer from 1 to 10, more preferably an integer from 2 to 10, and even more preferably an integer from 2 to 6.

[0048] m1 and m2 are each independent integers from 0 to 4, n' is an integer from 1 to 6, and the sum of m1, m2 and n' is from 1 to 8.

[0049] *-(CH2) n1 -O-(CH2) n2 In the given information, n1 and n2 are each an integer from 1 to 6, and the sum of n1 and n2 is from 2 to 10.

[0050] *-(CH2) n1 -NR-C (=O) -NR- (CH2) n2 In the given information, n1 and n2 are each an integer from 1 to 6, and the sum of n1 and n2 is from 2 to 9.

[0051] From the viewpoint of properly obtaining the effects of the present invention, *-L a -A-L a’ -*The following method is preferred. The definitions of m1, m2, n, n', n1, and n2 in the following formulas are the same as those in the formulas above. Furthermore, R in the following formulas represents a hydrogen atom or a monovalent organic group. In the case of two Rs, each independently has the above definition. Examples of monovalent organic groups that represent L as described above can be listed. a and L a’ The structure exemplified by R in -C(=O)-NR-.

[0052] *-(CH2) n -*、-O-(CH2) n -O-*; *-O-(CH2) n1 -O-(CH2) n2 -O-*; *-C(=O)-(CH2) n -C (=O) -*; *-C(=O)-NR-(CH2) n -O-*; *-O-C (=O)-(CH2) n -O-*; *-O-C (=O)-(CH2) n -O-C (=O)-*; *-O-C (=O)-(CH2) n -C (=O) -O -*; *-(CH2) m1 -O-C(=O)-(CH2) n’ -C(=O)-O-(CH2) m2 -*; *-S-(CH2) n -S-*; *-C(=O)-NR-(CH2) n -NR-C (=O)-*; *-C(=O)-O-(CH2) n -O-C (=O)-*; *-(CH2) m1 -C(=O)-O-(CH2) n’ -O-C(=O)-(CH2) m2 -*; *-O-(CH2) n -*、*-S-(CH2) n -*; *-NR-C (=O)-(CH2) n -C (=O) -NR -*; *-(CH2) n1 -NR-C (=O) -NR- (CH2) n2 -*.

[0053] Furthermore, from the viewpoint of properly obtaining the effects of the present invention, *-(CH2) is preferred. n -*、*-O-(CH2) n -O-*、*-O-(CH2) n -*.

[0054] The following compounds can be listed as specific examples of diamines in which L0 is a single bond.

[0055] 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, etc.

[0056] From the viewpoint of properly obtaining the effects of the present invention, the above-described structural unit (a-1Da) preferably has a divalent organic group as shown in any one of the following formulas (h1-1) to (h1-18).

[0057] In formulas (h1-1) to (h1-14), the bonding positions of the benzene ring are preferably at positions 1 and 4, and the bonding positions of the naphthalene ring are preferably at positions 2 and 6.

[0058] In formula (h1-4), the total number of -CH2- is less than 10.

[0059] In equations (h1-7) and (h1-8), the total number of -CH2- is 8 or less, and the two m can be either the same or different from each other.

[0060] It should be noted that the hydrogen atoms on the benzene ring, naphthalene ring, or aromatic heterocycle in the following formulas (h1-1) to (h1-13), (h1-15) to (h1-18) are optionally replaced by methyl, methoxy, or fluorine atoms. In one embodiment, polymer (A) preferably contains at least 1 mol% and more preferably at least 5 mol% of the aforementioned structural units (a-1Da) relative to 1 mole of all diamine-derived structural units in polymer (A). Furthermore, in another embodiment, polymer (A) preferably contains at least 100 mol% and more preferably at least 90 mol% and even more preferably at least 80 mol% of the aforementioned structural units (a-1Da) relative to 1 mole of all diamine-derived structural units in polymer (A).

[0061] The polymer (A) of the present invention may also have the following formula (2D) a The structural unit (a-2Da) shown is a structural unit derived from diamine. The structural unit (a-2Da) can be one or more types. (Formula (2D)) a ), Y a2 This indicates a divalent organic group derived from a diamine other than the specific diamine mentioned above. Z is synonymous with Z in the above formula (a-1Da), and the preferred embodiment is also the same as Z in the above formula (a-1Da).

[0062] The following substances can be listed as preferred specific examples of the other diamines mentioned above.

[0063] p-Phenylenediamine, 2,3,5,6-tetramethylp-phenylenediamine, 2,5-dimethylp-phenylenediamine, m-phenylenediamine, 2,4-dimethylm-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 and a primary amino group (preferably 4-(2-(methylamino)ethyl)aniline) (here, a 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; 1,4-Phenylidene bis(4-aminobenzoate), 1,4-Phenylidene bis(3-aminobenzoate), 1,3-Phenylidene bis(4-aminobenzoate), 1,3-Phenylidene bis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl) isophthalate, bis(3-aminophenyl) isophthalate; 4,4'-Diaminoazobenzene, diaminodiphenylacetylene, 4, 4-Diaminochalcone, or aromatic diamines with cinnamic acid ester structures represented by [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]prop-2-enyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate] Diamines with photooriented groups; diamines with photopolymerizable groups at the ends, such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallyl aniline; diamines with free radical polymerization initiator functions, such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropionanone and 2-(4-(2-hydroxy-2-methylpropionyl)phenoxy)ethyl-3,5-diaminobenzoate; diamines with amide bonds, such as 4,4'-diaminobenzoylaniline; diamines with urea bonds, such as 1,3-bis(4-aminophenyl)urea; H2N-Y D -NH2(Y DThis refers to diamines containing a divalent organic group (-N(D)-, where D represents a protecting group that is removed and replaced by a hydrogen atom upon heating) or other thermally detachable groups; 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'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, etc. 1,4-Aminophenyl)silane, dimethylbis(3-aminophenyl)silane, 4,4'-thiodiphenylamine, 3,3'-thiodiphenylamine, 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, 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-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]-aniline, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-oxazolyl]-benzyl Amines, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 2,5-bis(4-aminophenyl)pyrrole, 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[aniline], 1,4-bis-(4-aminophenyl)piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 5,4'-diaminobenzimidazole, 5-(1H-benzimidazole-2-yl)phenyl-1,3-diamine, or heterocyclic diamines such as those shown in formulas (z-1) to (z-17), (z-19) to (z-21), or 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-phenylenediamine, etc. A diamine, represented by an amine structure, has at least one nitrogen-containing structure selected from the group consisting of a heterocycle, a secondary amino group, or a tertiary amino group containing a nitrogen atom (excluding amino groups derived from -N(D)- (where D represents a protecting group that is removed and substituted with a hydrogen atom by heating). Hereinafter, it is also referred to as a specific nitrogen-containing structure. A specific nitrogen-containing structure is a diamine (excluding specific diamines) containing groups other than the two amino groups involved in the condensation reaction; 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'-Diaminodiphenylether-3,3'-dicarboxylic acid, and other diamines with carboxyl groups; 1 -(4-aminophenyl)-1,3,3-trimethyl-1H-indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-6-amine; 1,3-bis(3-aminopropyl)-tetramethyldisiloxane and other diamines having siloxane bonds; acyclic aliphatic diamines such as m-phenylenediamine, 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 with two amino groups bonded to any one of the groups shown in formulas (Y-1) to (Y-167) as described in WO2018 / 117239. X in (z-13) 13 (Indicates methyl or phenyl). (In formula (z-19), X) 19 Represents -C (=O)-, -O-, or -NH-. R 19 R 19’ Each can independently represent a hydrogen atom or a methyl group. In formula (z-22), X 22 It represents -CH2-, -(CH2)3-, or -NH-.

[0064] It should be noted that the D in -N(D)- is preferably a carbamate organic group represented by benzyloxycarbonyl, 9-fluorenyloxycarbonyl, allyloxycarbonyl, tert-butyloxycarbonyl (hereinafter also referred to as "Boc group"). From the viewpoints of good efficiency of thermal removal, removal at a relatively low temperature, and emission in the form of harmless gas during removal, the Boc group is particularly preferred.

[0065] As the diamine having the aforementioned thermally detachable group, it is preferably selected from the following formula (d Da-1) ~ (d) Da The diamine in -18). (Formula (d) Da -2), (d) Da -6), (d) Da In (-7), R represents a hydrogen atom or a Boc group. In one embodiment, when the polymer (A) used in this invention has the aforementioned structural unit (a-2Da), it preferably contains 10 mol% or more, more preferably 20 mol% or more of the structural units derived from the aforementioned other diamines, relative to 1 mole of all diamine-derived structural units contained in the polymer (A). It preferably contains 99 mol% or less, more preferably 95 mol% or less of the aforementioned structural units (a-2Da), relative to 1 mole of all diamine-derived structural units contained in the polymer (A).

[0066] Furthermore, from the viewpoint of improving the two-layer separability between the two polymers, polymer (A) may also contain structural units derived from the aforementioned diamine with thermally detachable groups as the aforementioned structural units (a-2Da). Relative to 1 mole of all diamine-derived structural units contained in polymer (A), the structural units derived from the aforementioned diamine with thermally detachable groups are preferably 5 mol% or more. Relative to 1 mole of all diamine-derived structural units contained in polymer (A), the structural units derived from the aforementioned diamine with thermally detachable groups are preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less.

[0067] <Manufacturing of polyimide precursors or polyimides> In the polymer (A) contained in the liquid crystal alignment agent of the present invention, the above formula (1T) a Polyamic acids in which at least one of the R atoms is a hydrogen atom can be manufactured, for example, by the following method.

[0068] By reacting the tetracarboxylic dianhydride component with the diamine component, a polymer (polyamic acid) with an amic acid structure can be obtained. Polyamic acid has the above formula (1D...). a In the case of the structure shown, for example, as a diamine component, a structure having -N(Z)-Y is used. a -N(Z)- structure (Y a The definition of Z is the same as above. Furthermore, as a tetracarboxylic acid derivative component, a diamine with X is used. a (X) a (The definition is the same as above) Tetracarboxylic acid dianhydride.

[0069] For detailed synthesis methods of polyimide precursors and polyimides, please refer to, for example, WO2015 / 012368.

[0070] When manufacturing the polyimide precursor and polyimide of this invention, a suitable capping agent can also be used with a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivatives and a diamine component containing a diamine to manufacture a capped polymer. The capped polymer has the effect of increasing the film hardness of the liquid crystal alignment film obtained from the coating and improving the adhesion properties between the sealant and the liquid crystal alignment film.

[0071] Examples of polyimide precursors and ends of polyimides in this invention include: amino, carboxyl, anhydride, or groups derived from the capping agent described later. Amino, carboxyl, and anhydride groups can be obtained through conventional condensation reactions or by capping with the following capping agents.

[0072] Examples of capping agents include: acetic anhydride, maleic anhydride, succinic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride, etc.; di-tert-butyl dicarbonate, diallyl dicarbonate, etc.; acryloyl chloride, methyl... Chlorocarbonyl compounds such as acryloyl chloride and nicotinyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine; and isocyanates with unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc.

[0073] The proportion of the capping agent used is preferably 0.01 to 20 moles, more preferably 0.01 to 10 moles, relative to a total of 100 moles of diamine components used.

[0074] The weight-average molecular weight (Mw) of the polyimide precursor and polyimide, converted from polystyrene by gel permeation chromatography (GPC), is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn) shown by the ratio of Mw to the number-average molecular weight (Mn) of polystyrene determined by GPC is preferably 15 or less, more preferably 10 or less. By maintaining this molecular weight range, good liquid crystal alignment of the liquid crystal display element can be ensured.

[0075] <Polymer solution viscosity / molecular weight> When the polymer (A) used in this invention is prepared into a solution with a concentration of 10-15% by mass, from an operational point of view, it is preferably preferred to have a solution viscosity of, for example, 10-1000 mPa•s. It should be noted that the above-mentioned solution viscosity (mPa•s) of the polymer is a value obtained by measuring a 10-15% by mass polymer solution prepared at 25°C using an E-type rotational viscometer with a good solvent (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0076] The weight-average molecular weight (Mw) of the polymer (A) as determined by gel permeation chromatography (GPC) based on polystyrene is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn) shown by the ratio of Mw to the number-average molecular weight (Mn) of polystyrene as determined by GPC is preferably 15 or less, more preferably 10 or less. By maintaining this molecular weight range, good orientation and stability of the liquid crystal display element can be ensured.

[0077] The liquid crystal alignment agent of the present invention may also contain polymers other than polymer (A). Specific examples of other polymers include at least one polymer (hereinafter also referred to as "polymer (Q)") selected from the group consisting of a polyimide precursor other than polymer (A) and a polyimide as an imide derivative of the polyimide precursor, polymers selected from the group consisting of polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates.

[0078] From the viewpoint of properly obtaining the effects of the present invention, polymer (Q) is more preferably polymer (B) as described later.

[0079] Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), and GSM301 (manufactured by Gifu Shellac Manufacturing); specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAM-600 (manufactured by Kuraray); and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).

[0080] Other polymers may be used alone or in combination of two or more. The proportion of other polymers relative to 100 parts by mass of the polymer component in the liquid crystal alignment agent is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass.

[0081] It should be noted that, in this specification, polymer component refers to the collective term for polymer (A) contained in the liquid crystal alignment agent, as well as other polymers besides polymer (A) added as needed. When the liquid crystal alignment agent contains only polymer (A), polymer component refers to polymer (A).

[0082] <Polymer (B)> The liquid crystal alignment agent of the present invention may also be combined with the above-described polymer (A), comprising a polyimide precursor selected from the group consisting of a polyimide precursor having structural units derived from tetracarboxylic acid derivatives and structural units derived from diamines, and an imidized polymer being an imidized product of the polyimide precursor, and comprising the following formula (1T) b The structural unit (b-1Tb) shown is used as a structural unit derived from a tetracarboxylic acid derivative in polymer (B) (hereinafter also referred to as "polymer (B)"). It should be noted that polymer (A) and polymer (B) are different polymers.

[0083] Polymer (B) may be composed of one or more of the above-mentioned structural units constituting polymer (B). In addition, each of the above-mentioned structural units constituting polymer (B) may also be composed of one or more of the above-mentioned structural units. (Formula (1T)) b In ), X b This indicates a tetravalent organic group derived from a tetracarboxylic acid dianhydride. Formula (1D) b ), Y b This represents a divalent organic group derived from a diamine. Z is related to the above formula (1D). a Z is synonymous with ). R is synonymous with the above formula (1T) a Z is synonymous with . <Polymer (B)> (The structural units of polymer (B) derived from tetracarboxylic acid derivatives) The polyimide precursor in the polymer (B) of the present invention has the above formula (1T) b The structural unit (b-1Tb) shown is a structural unit derived from a tetracarboxylic acid derivative.

[0084] As provided by the above formula (1T) b X b The tetravalent organic group can be exemplified by the tetravalent organic group obtained by removing two anhydride groups (-C(=O)-O-C(=O)-) from the tetracarboxylic dianhydride exemplified in polymer (A).

[0085] From the viewpoint of properly obtaining the effects of the present invention, polymer (B) preferably contains more than 40 mol% and more preferably more than 50 mol% of structural units (b-1Tb) relative to 1 mole of all structural units derived from tetracarboxylic acid derivatives contained in polymer (B).

[0086] (The diamine-derived structural units of polymer (B)) The polymer (B) of the present invention has the following formula (1D) b The structural unit (b-1Db) shown above is a structural unit derived from diamine. The structural unit (b-1Db) can be one or more types. b The Z-valent organic group in ) is related to the above formula (1D) a Z is synonymous with ). (Formula (1D)) b ), Y b This represents a divalent organic group derived from a diamine. Z is related to the above formula (1D). a Z is synonymous with . As the above equation (1D) b Preferred specific examples of diamines in polymer (A) can be listed as diamines exemplified in polymer (A).

[0087] From the perspective of minimizing residual DC, in polymer (B), the aforementioned Y b Preferably, the divalent organic group is obtained by removing two amino groups from a diamine selected from the group consisting of the above-mentioned semi-aromatic diamines, diamines having urea bonds (e.g., a specific diamine where A is a divalent organic group (q2), or a diamine having urea bonds exemplified among the above-mentioned other diamines), diamines having amide bonds, diamines having a specific nitrogen-containing atom structure, diamines having a carboxyl group, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, p-phenylenediamine, and m-phenylenediamine (these are collectively referred to as "specific divalent organic groups (b)").

[0088] From the perspective of minimizing residual DC, polymer (B) may contain 5 mol% or more, 10 mol% or more, or 20 mol% or more of the aforementioned Y, relative to 1 mole of all diamine-derived structural units in polymer (B). b For the specific divalent organic group (b) mentioned above, the formula (1D) bThe structural unit (b-1Db) is shown in the figure. In addition, the content of the structural unit (b-1Db) relative to 1 mole of all structural units derived from diamine in polymer (B) can be less than 100 mol% or less, or less than 90 mol%.

[0089] As the above equation (1D) b The Z-valent organic group in the above formula (1D) can be listed as an example. a The structure exemplified by Z in ).

[0090] In the liquid crystal alignment agent of the present invention, from the viewpoint of having less residual image from residual DC, the content ratio of polymer (A) to polymer (B) in terms of the mass ratio of [polymer (A) / polymer (B)] can be 10 / 90 to 90 / 10, 20 / 80 to 90 / 10, or 20 / 80 to 80 / 20.

[0091] <(B) Component> The liquid crystal alignment agent of the present invention contains compound (B) as shown in formula (1). (In equation (1), Ar1 and Ar) 1’ Each of the following independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, wherein one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring are optionally substituted by a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2).

[0092] *-X1-(Y1-L) n -Y2-X2-* (2) (In equation (2), X1 and X2 independently represent single bonds, -O-, *1-O-CO-*2 (*1 and *2 represent bonded bonds, *1 and Ar1 or Ar) 1’ (Bonding). L represents a single bond, -O-, -O-C(=O)-, or -C(=O)-O-. In the presence of multiple Ls, the Ls may optionally be the same or different from each other. At least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer from 1 to 6. Y1 and Y2 each independently represent a divalent hydrocarbon group with 1 to 6 carbon atoms, wherein a portion of the hydrogen atoms in the divalent hydrocarbon group may optionally be substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group. In the presence of multiple Y1s, the multiple Y1s may optionally be the same or different from each other. * indicates a bond with Ar1 or Ar 1’(The bonded bond). Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4) and maleimide group. It should be noted that when there are multiple (q1) to (q4) in formula (1), the multiple R1 to R4 may optionally be the same or different from each other. (In formula (q1), R1 represents a monovalent organic group, which is derived from a carbonyl group, a sulfonyl group, and *1-C(R) group.) q1 Any linking group in )2-*2 is bonded to a nitrogen atom. R2 represents a hydrogen atom or a monovalent organic group. *1-C(R q1 In )2-*2, *1 represents the bond with a nitrogen atom, and multiple R q1 Each R independently represents a hydrogen atom or a monovalent organic group. Multiple Rs q1 They may be identical or different from each other. *1-C(R) q1 In formula (q2), *2 is bonded to a monovalent organic group containing a heteroatom. Examples of heteroatom-containing groups include hydroxyl, carboxyl, or epoxy groups. In formula (q2), R3 represents a hydrogen atom or a monovalent organic group. In formula (q3), R4 represents a hydrogen atom, hydroxyl, halogen atom, or a monovalent organic group. In formula (q4), R5 represents a hydrogen atom, hydroxyl, or a monovalent organic group. When Q or Q' represents a maleimide group, Q or Q' is bonded to Ar1 or Ar via the nitrogen atom in that maleimide group. 1’ Bonding.

[0093] As monovalent organic groups in R1 of the above formula (q1), examples include: monovalent hydrocarbon groups with 1 to 30 carbon atoms; monovalent groups (R1) formed by replacing the methylene group of the hydrocarbon group with -O-, -S-, -CO-, -COO-, -COS-, -NR6-, -CO-NR6-, -Si(R6)2- (wherein, in the presence of multiple R6 groups, each is independently a hydrogen atom or a monovalent organic group with 1 to 6 carbon atoms), -SO2-, etc. 1b ); the above monovalent hydrocarbon group or the above monovalent group (R) 1b A monovalent group formed by replacing at least one of the hydrogen atoms bonded to a carbon atom with a substituent (x); a monovalent group having a heterocyclic structure. Wherein, R1 is derived via a carbonyl group, a sulfonyl group, and *1-C(R q1 Any linking group in )2-*2 is bonded to a nitrogen atom.

[0094] As monovalent organic groups in R2 of formula (q1), R3 of formula (q2), R4 of formula (q3), and R5 of formula (q4), examples include: monovalent hydrocarbon groups with 1 to 30 carbon atoms; monovalent groups formed by replacing the methylene group of the hydrocarbon group with -O-, -S-, -CO-, -COO-, -COS-, -NR6-, -CO-NR6-, -Si(R6)2- (wherein, in the presence of multiple R6 groups, each is independently a hydrogen atom or a monovalent organic group with 1 to 6 carbon atoms), -SO2-, etc. b ); the above monovalent hydrocarbon group or the above monovalent group (R) b A monovalent group formed by replacing at least one of the hydrogen atoms bonded to a carbon atom with a substituent (x); a monovalent group having a heterocyclic ring.

[0095] Examples of substituents (x) mentioned above include: halogen atom, hydroxyl group, nitro group, amino group, mercapto group, nitroso group, silanol group, sulfinyl group, phospho group, carboxyl group, cyano group, and sulfonyl group.

[0096] In the above formula (2), Y1 and Y2 are each independently a divalent hydrocarbon group with 1 to 6 carbon atoms. Examples of such divalent hydrocarbon groups include linear or branched alkylene groups, -CH=CH-, phenylene groups, or cyclohexylene groups, but are not limited to these.

[0097] From the viewpoint of properly obtaining the effects of the present invention, Y1 and Y2 are preferably hydrocarbon groups having 2 to 6 carbon atoms, more preferably alkylene groups having 2 to 4 carbon atoms, and even more preferably alkylene groups having 2 or 4 carbon atoms.

[0098] A portion of the hydrogen atom in the divalent hydrocarbon group is optionally replaced by a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group, preferably a fluorine atom, as the halogen atom replacing the hydrogen atom in the divalent hydrocarbon group. In the presence of multiple Y1 groups, the multiple Y1 groups may optionally be the same as or different from each other.

[0099] L represents -O-, -C(=O)-, -O-C(=O)-, or -C(=O)-O-. In the presence of multiple L's, these L's can be chosen to be the same as or different from each other.

[0100] Wherein, at least one L represents -O-C (=O)- or -C (=O)-O-, preferably at least two L represent -O-C (=O)- or -C (=O)-O-. n is an integer from 1 to 6, preferably an integer from 1 to 4, more preferably an integer from 2 to 4, and even more preferably an integer of 2 or 4.

[0101] As the group "*-(Y1-L) in the above formula (2) n More preferred specific examples of “-Y2-*” can be listed below.

[0102] *-(CH2) p -O-C(=O)-(CH2) q -C(=O)-O-(CH2) r -*; *-(CH2) p -C(=O)-O-(CH2) q -O-C(=O)-(CH2) r -*; *-(CH2) n1 -O-C(=O)-(CH2) n2 -C(=O)-O-(CH2) n3 -O-C(=O)-(CH2) n4 -C(=O)-O-(CH2) n5 -*; *-(CH2) n1 -C(=O)-O-(CH2) n2 -O-C(=O)-(CH2) n3 -C(=O)-O-(CH2) n4 -O-C(=O)-(CH2) n5 -*; In the above structure, p, q, and r are each an independent integer from 1 to 6.

[0103] n1 to n5 are each an independent integer from 1 to 6. Among them, when n1 to n5 are integers from 1 to 6, the total number of carbon atoms in the divalent hydrocarbon group is 20 or less.

[0104] As a preferred specific example of formula (q1), the following can be listed: *-NH-C(=O)-R O (R) O (This indicates a monovalent organic group bonded to a carbonyl group via an oxygen atom); *-NH-C(=O)-R N (where R) N (This indicates a monovalent organic group bonded to a carbonyl group via a nitrogen atom); *-NH-C(=O)-R C (Where Rc represents a monovalent organic group bonded to a carbon atom via a carbonyl group); *-NH-(CH2) n -OH (n is an integer from 1 to 6); or the following formula (q1-a) to (q1-d). As a preferred specific example of R0, an organic group obtained by removing a hydrogen atom from the hydroxyl group of an alcohol, oxime, or phenol compound can be listed.

[0105] As RN Preferred specific examples may include organic groups obtained by removing a hydrogen atom from a nitrogen atom of a nitrogen-containing compound such as a lactam compound, amine compound, pyrazole compound, imidazole compound, or imide compound.

[0106] As R C Preferred specific examples may include alkyl groups, alkenyl groups, organic groups obtained by removing a hydrogen atom from the carbon atom of an active methylene compound, or -(CH2). n -COOH (n is an integer from 1 to 6).

[0107] Examples of the aforementioned alcohol compounds include: methanol, ethanol, propanol, butanol (preferred examples include n-butanol, isobutanol, sec-butanol, tert-butanol, etc.), cyclohexanol, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, and saturated alcohols such as lactic acid esters; non-cyclic unsaturated alcohols such as allyl alcohol; and alcohols with aromatic rings such as benzyl alcohol and 9-fluorenylmethanol.

[0108] Examples of the aforementioned oxime compounds include acetone oxime, formaldehyde oxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.

[0109] Examples of the aforementioned lactam compounds include ε-caprolactam and γ-butyrolactam.

[0110] Examples of the aforementioned phenolic compounds include phenol, naphthol, cresol, xylenol, and halogenated phenols.

[0111] Primary and secondary amines can be listed as examples of the aforementioned amine compounds. The amine compounds can be any of aromatic amines, aliphatic amines, or alicyclic amines, and examples include: monoalkylamines (methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.), dialkylamines (preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, methylethylamine, methylpropylamine, ethylpropylamine), H2N(Boc), HN(Boc)2, etc.

[0112] Examples of the aforementioned active methylene compounds include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

[0113] Examples of the aforementioned pyrazole compounds include pyrazole, methylpyrazole, and dimethylpyrazole.

[0114] Examples of the imidazole compounds mentioned above include: imidazole, 1-methylimidazolium, 1-ethylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, etc.

[0115] Examples of the aforementioned imide compounds include maleimide, succinimide, phthalimide, and their derivatives.

[0116] Preferred specific examples of R3 in formula (q2) include: hydrogen atom; straight-chain alkyl group with 1 to 6 carbon atoms; alkenyl group with 2 to 6 carbon atoms; carbamate organic groups represented by benzyloxycarbonyl, 9-fluorenyloxycarbonyl, allyloxycarbonyl, Boc group, etc.; glycidyl group; epoxycyclohexylmethyl group (preferably 2,3-epoxycyclohexylmethyl or 3,4-epoxycyclohexylmethyl); group having an oxetane ring as shown in the following formula (q2-a); N-hydroxysuccinimide ester group. (In formula (q2-a), R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 6 carbon atoms).

[0117] As preferred specific examples of R4 in formula (q3), the following can be listed: hydroxyl group; -OR q3 (R) q3 The group may be an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, or a group having an aromatic ring (e.g., benzyl, 9-fluorenylmethyl, etc.); glycidyl group; cyclohexyl epoxide (preferably 2,3-cyclohexyl epoxide or 3,4-cyclohexyl epoxide); or a group having an oxetane ring as shown in formula (q2-a) above.

[0118] As preferred specific examples of formula (q4), the following can be listed: hydroxyalkyl groups (preferably hydroxymethyl groups) with 1 to 6 carbon atoms, and aliphatic carboxyl groups with 2 to 6 carbon atoms.

[0119] As a monovalent group that replaces the benzene ring, the biphenyl structure, or the hydrogen atom on the naphthalene ring in Ar and Ar' of the above formula (1), examples include: halogen atoms, alkyl groups with 1 to 3 carbon atoms, alkenyl groups with 2 to 3 carbon atoms, cyano groups, nitro groups, etc.

[0120] As the above-mentioned compound (B), it is preferred to be at least one compound selected from the group consisting of the following formulas (q1-1) to (q1-5), (q2-1) to (q2-3), (q3-1) to (q3-3) and (q4-1) to (q4-2). In the liquid crystal alignment agent of the present invention, the preferred content of compound (B) shown in the above formula (1) is 0.1 to 50 parts by mass relative to 100 parts by mass of polymer (A), and more preferably 0.1 to 30 parts by mass.

[0121] <Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention is used to manufacture liquid crystal alignment films, and from the viewpoint of forming a uniform thin film, it is adopted in the form of a coating liquid. For the liquid crystal alignment agent of the present invention, a coating liquid containing the above-mentioned polymer components and solvent is also preferred.

[0122] The content (concentration) of the polymer component contained in the liquid crystal alignment agent of the present invention can also be appropriately changed according to the desired coating thickness. From the perspective of forming a uniform and defect-free coating, it is preferably 1% by mass or more relative to the total amount of the liquid crystal alignment agent, and from the perspective of the storage stability of the solution, it is preferably 10% by mass or less.

[0123] Regarding the proportion of polymer (A) in the liquid crystal alignment agent, from the viewpoint of appropriately obtaining the effects of this disclosure, it 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 polymer contained in the liquid crystal alignment agent. Regarding the proportion of polymer (A) in the case where the liquid crystal alignment agent contains other polymers, it 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 component contained in the liquid crystal alignment agent.

[0124] The solvent in a liquid crystal alignment agent is not particularly limited as long as it uniformly dissolves the polymer components. Specific examples include: N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactic acid, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-( N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (also collectively referred to as "good solvents"), etc. Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, or γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass.

[0125] Furthermore, the solvent contained in the liquid crystal alignment agent is preferably a mixed solvent that, in addition to the solvents mentioned above, also uses a solvent that improves the coatability and surface smoothness of the coating film when applying the liquid crystal alignment agent (also known as a poor solvent). Specific examples of the poor solvents used are described below, but are not limited thereto.

[0126] Examples include: diisopropyl ether, diisobutyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxyethyl acetate, 1-methylpentyl acetate, 2-ethylethyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisopentyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2- (2-Butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol 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, diisobutyl ketone (2,6-dimethyl-4-heptanone), etc. The content of undesirable solvents is preferably 1 to 80% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. The type and content of undesirable solvents should be appropriately selected based on the coating equipment, coating conditions, and coating environment of the liquid crystal alignment agent.

[0127] Among them, diisobutylmethanol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate or diisobutyl ketone are preferred.

[0128] Preferred solvent combinations for good and bad solvents include: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone and γ-butyrolactone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol monobutyl ether. Diethyl ether; N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether and diisobutyl ketone; N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone with γ-butyrolactone with propylene glycol monobutyl ether and diisobutyl methanol; N-methyl-2-pyrrolidone with γ-butyrolactone with dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone with propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc.

[0129] The liquid crystal alignment agent of the present invention may also contain additional components (hereinafter also referred to as additive components) other than polymer components and solvents. Examples of such additive components include: compounds for improving the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compounds, excluding compound (B)); adhesion promoters for improving the adhesion between the liquid crystal alignment film and the substrate, and the adhesion between the liquid crystal alignment film and the sealant; dielectrics and conductive substances for adjusting the dielectric constant and resistance of the liquid crystal alignment film; or imidization promoters for promoting imidization, etc.

[0130] Examples of such crosslinking compounds include at least one crosslinking compound selected from the group consisting of a crosslinking compound (c-1) having at least one substituent selected from epoxy group, oxacyclobutane, oxazoline structure, cyclic carbonate group, terminal isocyanate group, hydroxyl group and alkoxy group, and a crosslinking compound (c-2) having a polymerizable unsaturated group.

[0131] As preferred specific examples of the aforementioned crosslinking compounds (c-1) and (c-2), the following compounds can be listed. As compounds containing epoxy groups, examples 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, glycerol diglycidyl ether, dibromonepentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A type epoxy resins such as EPIKOTE 828 (manufactured by MITSUBISHI CHEMICAL), bisphenol F type epoxy resins such as EPIKOTE 807 (manufactured by MITSUBISHI CHEMICAL), and YX-8000 (manufactured by MITSUBISHI CHEMICAL). Hydrogenated bisphenol A type epoxy resins such as those manufactured by CHEMICAL (YX6954BH30, manufactured by MITSUBISHI CHEMICAL), epoxy resins containing a biphenyl backbone such as YX6954BH30, phenolic varnish type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co.), phenolic varnish type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co.), and tetra(glycidyloxymethyl) phenolic varnish type epoxy resins. Compounds in which tertiary nitrogen atoms are bonded to aromatic carbon atoms, such as 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, Compounds in which tertiary nitrogen atoms are bonded to aliphatic carbon atoms, such as 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, and 1,3,5-tris(N,N-diglycidylaminomethyl)benzene; isocyanurate compounds such as TEPIC (manufactured by Nissan Chemical Co., Ltd.); compounds described in paragraph 0037 of Japanese Patent Application Publication No. 10-338880; and compounds described in WO2017 / 170483, etc.; as compounds containing oxetane, examples include 1,4-bis{[(3-ethyl-3-oxetane)methoxy]methyl}benzene (ARON OXETANE OXT-121 (XDO)), bis[2-(3-oxetane)butyl] ether (ARON OXETANE), etc. OXT-221 (DOX), 1,4-bis[(3-ethyloxetane-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetane-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetane-3-yl)methoxy]benzene (CTOX), compounds having two or more oxetane groups as described in paragraphs 0170 to 0175 of WO2011 / 132751, etc.; as compounds having an oxazoline structure, examples include 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), etc.; such as E Polymers and oligomers containing oxazoline groups, such as POCROS (trade name, Nippon Shokubai Co., Ltd.); compounds described in paragraph 0115 of Japanese Patent Application Publication No. 2007-286597; and compounds containing cyclic carbonate groups, such as N,N,N',N'-tetratetra[(2-oxo-1,3-dioxolane-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N'-di[(2-oxo-1,3-dioxolane-4-yl)methyl]-1,3-phenylenediamine, and compounds described in paragraphs 0025 to 0030 and 0032 of WO2011 / 155577;Examples of compounds having terminal isocyanate groups include CORONATE AP stable M, CORONATE 2503, 2515, 2507, 2513, 2555, and MILLIONATE MS-50 (all manufactured by TOSOH); TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals); compounds having two or more protected isocyanate groups as described in paragraphs 0046 to 0047 of Japanese Patent Application Publication No. 2014-224978; and paragraphs 0119 to 012 of Japanese Patent Application Publication No. WO2015 / 141598. Compounds having three or more protected isocyanate groups, as described in section 0; examples of compounds having hydroxyl and / or alkoxy groups include N,N,N',N'-tetratetra(2-hydroxyethyl)hexamethylenediamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1 Compounds described in WO2015 / 072554, paragraph 0058 of Japanese Patent Application Publication No. 2016-118753, Japanese Patent Application Publication No. 2016-200798, and WO2010 / 074269, etc., are examples of crosslinking compounds having polymerizable unsaturated groups, including glyceryl mono(meth)acrylate, glyceryl di(meth)acrylate (a mixture of 1,2- and 1,3-type compounds), glyceryl tri(meth)acrylate, glycerol 1,3-diglyceryl glycol 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.

[0132] The above-described compound is an example of a cross-linking compound, but is not limited thereto. Examples include, for instance, components other than those described above, disclosed in paragraphs 0105 on page 53 to 0116 on page 55 of WO2015 / 060357. Furthermore, two or more cross-linking compounds may be combined.

[0133] When using a crosslinking compound, the content of the crosslinking compound in the liquid crystal alignment 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 alignment agent.

[0134] Examples of such sealing agents include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, and N-ethoxycarbonyl-3-aminopropyltrimethoxysilane. Methoxysilane, 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-diazanonylacetate, 9-triethoxysilyl-3,6-diazanonylacetate, N-benzyl-3-aminopropyltriethoxysilane N-Benzyl-3-aminopropyltriethoxysilane, N-Phenyl-3-aminopropyltrimethoxysilane, N-Phenyl-3-aminopropyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-Benzene Vinyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane, and other silane coupling agents.

[0135] When using an adhesive additive, the content of the adhesive additive in the liquid crystal alignment 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 alignment agent.

[0136] Examples of substances that can be used as dielectrics or conductors include monoamines with nitrogen-containing aromatic heterocycles, such as 3-pyridinemethylamine.

[0137] When using a dielectric or conductive substance, the content of the dielectric or conductive substance in the liquid crystal alignment 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 alignment agent.

[0138] The compounds used to promote imidization are preferably compounds having a basic site (e.g., primary amino group, aliphatic heterocycle (e.g., pyrrolidine skeleton), aromatic heterocycle (e.g., imidazole ring, indole ring), or guanidine group, etc.) (excluding the aforementioned crosslinking compounds and compounds used to adjust the dielectric constant and resistance of the liquid crystal alignment film), or compounds that generate the aforementioned basic site during calcination. More preferably, compounds that generate the aforementioned basic site during calcination are preferred. Specific examples of preferred compounds include amino acids in which some or all of the basic site is protected. Protecting groups for the basic site of the aforementioned amino acids include carbamate-based protecting groups such as the Boc group. Specific examples of the aforementioned amino acids include: glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, and ornithine. If we were to list more preferred examples of compounds for promoting imidization, we could include: N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butyloxycarbonyl)-L-histidine, or N-α-(tert-butyloxycarbonyl)-N-τ-(tert-butyloxycarbonyl)-L-histidine, etc.

[0139] The content of the compound for promoting imidization contained in the liquid crystal alignment agent of the present invention is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, more preferably 0.1 to 20 parts by mass, and even more preferably 5 to 20 parts by mass.

[0140] (Liquid crystal alignment film) The liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent of the present invention described above.

[0141] The manufacturing method of the liquid crystal alignment film of the present invention includes, for example, coating the above-mentioned liquid crystal alignment agent onto a substrate, firing it, and irradiating the obtained film with polarized radiation.

[0142] As a preferred embodiment of the manufacturing method of the liquid crystal alignment film of the present invention, a manufacturing method of the liquid crystal alignment film including the following steps can be listed, for example: a step of coating the above-mentioned liquid crystal alignment agent onto a substrate (step (1)); a step of firing the coated liquid crystal alignment agent (step (2)); and a step of aligning the film obtained in step (2) as appropriate (step (3)).

[0143] <Process (1)> As for the substrate used in this invention for coating the liquid crystal alignment agent, there are no particular limitations as long as it is a highly transparent substrate; glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and other plastic substrates can also be used. In this case, using a substrate with ITO (Indium Tin Oxide) electrodes for driving the liquid crystal is preferable from a process simplification perspective. Furthermore, in reflective liquid crystal display elements, if it is a single-sided substrate, an opaque material such as a silicon wafer can be used, and the electrodes can be made of light-reflecting materials such as aluminum. Moreover, in the case of manufacturing liquid crystal display elements using IPS or FFS driving methods, a substrate with electrodes formed of a transparent conductive film or metal film patterned in a comb-like shape and a counter substrate without electrodes are used.

[0144] Methods for coating a liquid crystal alignment agent onto a substrate and forming a film include screen printing, offset printing, flexographic printing, inkjet printing, and spraying. Among these, inkjet printing is preferred.

[0145] <Process (2)> Step (2) is a step of firing the liquid crystal alignment agent coated on the substrate to form a film. After the liquid crystal alignment agent is coated on the substrate, the solvent can be evaporated using a heating unit such as a heating plate, a thermal cycling oven, or an IR (infrared) oven; or thermal imidization of the amyl acid or amyl ester in the polymer can be performed. The drying and firing steps after coating the liquid crystal alignment agent of the present invention can be performed at any temperature and time, and can be performed multiple times. As for the temperature at which the solvent of the liquid crystal alignment agent is evaporated, the temperature of the heating unit can be, for example, between 40 and 180°C, but from the viewpoint of shortening the process, it can be performed between 40 and 150°C. The firing time is not particularly limited, for example, between 1 and 10 minutes, preferably between 1 and 5 minutes. In the case where, in addition to the step of evaporating the solvent, a step of thermal imidization of the amyl acid in the polymer is also performed, the following step can be performed after the step of evaporating the solvent: firing can be further performed at a temperature of, for example, between 150 and 300°C, preferably in the temperature range of 150 and 250°C. The firing time in the thermal imidization process is not particularly limited, but is, for example, 5 to 40 minutes, preferably 5 to 30 minutes.

[0146] If the film after firing is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, 5 to 300 nm is preferred, and 10 to 200 nm is more preferred.

[0147] <Process (3)> Step (3) is a step of aligning the film obtained in step (2). Examples of alignment methods for liquid crystal alignment films include rubbing or photo-alignment, but photo-alignment is preferred. As a photo-alignment method, the following method can be used: irradiating the surface of the film with radiation polarized in a fixed direction, followed by heating treatment as appropriate, to impart liquid crystal alignment properties (also called liquid crystal alignment capability). As the radiation, ultraviolet light or visible light with a wavelength of 100–800 nm can be used. Ultraviolet light with a wavelength of 100–400 nm is preferred, and ultraviolet light with a wavelength of 200–400 nm is more preferred.

[0148] The preferred radiation dose is 1–400 mJ / cm². 2 More preferably 10–300 mJ / cm 2 More preferably, it is 50–250 mJ / cm 2 .

[0149] As a light source for illumination, for example, 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 (such as KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (such as sodium lamps), microwave-excited electrodeless lamps, etc.

[0150] Furthermore, when polarized light is used as the irradiation light, the higher the extinction ratio of the polarized light, the higher the anisotropy it imparts. Therefore, for example, in the case of ultraviolet light, the extinction ratio of polarized ultraviolet light is more preferably 10:1 or more, and even more preferably 20:1 or more.

[0151] Furthermore, to improve liquid crystal alignment when irradiated with radiation, the substrate having the film can be heated at 50–250°C while being irradiated. The liquid crystal alignment film produced in this way allows the liquid crystal molecules to be stably aligned in a fixed direction.

[0152] Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can also be contacted with a solvent, or the liquid crystal alignment film irradiated with radiation can be heated.

[0153] The heat treatment of the above-mentioned radiation-irradiated coating is preferably performed at 50 to 300°C for 1 to 30 minutes, and more preferably at 120 to 250°C for 1 to 30 minutes.

[0154] (Liquid crystal display element) The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention.

[0155] From the viewpoint of obtaining high liquid crystal alignment, the liquid crystal alignment film of the present invention is preferred as a liquid crystal alignment film for liquid crystal display elements of lateral electric field type such as IPS type and FFS type, and in particular, it is useful as a liquid crystal alignment film for liquid crystal display elements of FFS type.

[0156] Liquid crystal display elements can be manufactured by: after obtaining a substrate with a liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention, fabricating a liquid crystal cell by a known method, and dispensing liquid crystal into the liquid crystal cell. Specifically, the following two methods can be listed.

[0157] In the first method, two substrates are first arranged opposite each other with their respective liquid crystal alignment films facing each other, separated by a gap (cell gap). Next, the peripheries of the two substrates are bonded together using a sealant. After injecting a liquid crystal composition into the cell gap defined by the substrate surfaces and the sealant and bringing it into contact with the film surface, the injection hole is sealed.

[0158] The second method is known as the ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined area on one of two substrates on which a liquid crystal alignment film has been formed. A liquid crystal composition is then dropped onto several predetermined locations on the surface of the alignment film. The other substrate is then bonded together with the alignment films facing each other, and the liquid crystal composition is spread across the entire surface of the substrate, bringing it into contact with the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant.

[0159] Regardless of whether the first or second method is used, it is ideal to further heat the liquid crystal composition to a temperature at which it becomes an isotropic phase, and then slowly cool it to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0160] It should be noted that when the coating has undergone a friction treatment, the two substrates are arranged at a predetermined angle to each other with the friction directions of their respective coatings, for example, in an orthogonal or antiparallel configuration. Similarly, when a photo-alignment treatment has been performed, the substrates are arranged at a predetermined angle to each other with their alignment directions, for example, in an orthogonal or antiparallel configuration.

[0161] As a sealant, epoxy resin containing a curing agent and alumina spheres as spacers can be used, for example. Nematic liquid crystals and smectic liquid crystals can be cited as examples, with nematic liquid crystals being preferred.

[0162] There are no particular limitations on the liquid crystal composition. Any of the following can be used: a composition containing at least one liquid crystal compound (liquid crystal molecule) with positive dielectric anisotropy (also called positive liquid crystal composition, positive liquid crystal), or a liquid crystal composition with negative dielectric anisotropy (also called negative liquid crystal composition, negative liquid crystal), preferably a negative liquid crystal composition.

[0163] The liquid crystal composition described above may contain liquid crystal compounds having fluorine atoms, hydroxyl groups, amino groups, fluorine-containing groups (e.g., trifluoromethyl), cyano groups, alkyl groups, alkoxy groups, alkenyl groups, isothiocyanate groups, heterocyclic groups, cycloalkanes, cycloolefins, steroidal skeletons, benzene rings, or naphthyl rings. It may also contain compounds with two or more rigid sites (liquid crystal proto-skeleton) exhibiting liquid crystal properties (e.g., bimectic compounds formed by two rigid biphenyl structures or terphenyl structures linked by an alkyl group). The liquid crystal composition may be a nematic liquid crystal composition, a smectic liquid crystal composition, or a cholesteric liquid crystal composition.

[0164] Furthermore, from the viewpoint of improving liquid crystal orientation, the above-mentioned liquid crystal composition may be further supplemented with additives. Such additives include: photopolymerizable monomers such as compounds having polymerizable groups, optically active compounds (e.g., S-811 manufactured by MERCK), antioxidants, ultraviolet absorbers, pigments, defoamers, polymerization initiators, or polymerization inhibitors.

[0165] Examples of positive liquid crystal displays include: ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by MERCK.

[0166] 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.

[0167] In addition, in PSA mode, MLC-3023 manufactured by MERCK is an example of a liquid crystal containing a compound with polymerizable groups.

[0168] Next, the polarizing plates are set. Specifically, a pair of polarizing plates are attached to the surfaces of the two substrates opposite to the liquid crystal layer. Examples of polarizing plates include: a polarizing plate made by sandwiching a polarizing film called an "H film" that absorbs iodine while stretching and oriented polyvinyl alcohol with a cellulose acetate protective film, or a polarizing plate made of the H film itself.

[0169] Example The present invention will be further described in detail below with reference to examples, but the invention is not limited to these examples. The abbreviations of the compounds used and the methods for determining their properties are described below.

[0170] (Organic solvent) NMP: N-methyl-2-pyrrolidone GBL: γ-Butyrolactone BCS: Butyl Solvent THF: Tetrahydrofuran (Tetracarboxylic acid dianhydride) CA-1 to CA-4: These are compounds represented by the formulas (CA-1) to (CA-4) below. (Diamine) DA-1 to DA-8: Compounds represented by the formulas (DA-1) to (DA-8) below, respectively. (additive) AD-1 to AD-11: Compounds represented by the formulas (AD-1) to (AD-11) respectively. Of the above additives, AD-3 to AD-7, AD-10 and AD-11 are included within the range of specific additives equivalent to compound (B) of this application.

[0171] (Reaction reagents) Boc2O: Ditert-butyl dicarbonate SAH: Succinic anhydride Ac2O: Acetic anhydride <Viscosity Measurement> The measurements were performed using a TVE-22H type E viscometer (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL and a conical rotor TE-1 (1°34', R24), at a temperature of 25°C.

[0172] <Determination of molecular weight> Mn and Mw were calculated using polyethylene glycol / polyethylene oxide conversion values ​​by performing the determination under the following conditions using the ambient temperature GPC (gel permeation chromatography) apparatus.

[0173] GPC device: GPC-101 (manufactured by Resonac (formerly Showa Denko) Co., Ltd.) Chromatographic columns: GPC KD-803 and GPC KD-805 (manufactured by Resonac (formerly Showa Denko)) in tandem. Column temperature: 50℃ Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr•H2O) 30 mmol / L, phosphoric acid•anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L) Flow rate: 1.0 mL / min Standard sample for standard curve plotting: EasiVial PEG / PEO polyethylene glycol / polyethylene oxide PL2080-0201 (molecular weight: approx. 1500, approx. 4000, approx. 13000, approx. 30000, approx. 70000, approx. 130000, approx. 500000, approx. 1000000, approx. 1500000) (manufactured by GL Sciences).

[0174] [Synthesis of monomers] DA-8 is a novel compound not disclosed in the literature. The product of the monomer synthesis example 1 below was synthesized by... 1 Identification was performed using H-NMR analysis. The analytical conditions are described below.

[0175] Device: BRUKER ADVANCE III - 500MHz Determination solvent: deuterated dimethyl sulfoxide (DMSO-d6) Reference material: Tetramethylsilane (TMS) 1 (H δ 0.0ppm) <Monomer Synthesis Example 1: Synthesis of DA-8> THF (600 g), 4-dimethylaminopyridine (DMAP, 16.6 g, 13.6 mmol), and succinic anhydride (34.1 g, 341 mmol) were added to 2-(4-nitrophenoxy)ethanol (50.0 g, 273 mmol), and the mixture was stirred at 50 °C. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC•HCl, 59.8 g, 312 mmol) and 1,4-butanediol (11.7 g, 130 mmol) were added to the resulting solution, and the mixture was stirred at room temperature (25 °C) for 3 hours. After the reaction was complete, water (1.5 kg) was added to precipitate crystals. The filtered solid was dried to obtain crude crystals. THF (300 g) was added to the crude crystals, and the mixture was heated and stirred at 65 °C. After cooling to room temperature, methanol (1.5 kg) was added for recrystallization. The filtered crystals were dried to obtain DA-8-1 (yield: 60.4 g, 97.2 mmol, 75%).

[0176] In DMSO-d6 1H-NMR (500MHz): δ (ppm) = 8.21 (d, J = 9.2Hz, 4H), 7.17 (d, J = 9.2Hz, 4H), 4.37 (q, 8H), 3.99 (s, 4H), 2.58 (m, 8H), 1.57 (m, 4H).

[0177] THF (1.2 kg) was added to the obtained DA-8-1 (60.3 g, 97.2 mmol), and after nitrogen purging, carbon-supported palladium (5% Pd carbon powder (containing water), K type, manufactured by NE Chemcat) (6.0 g) was added, followed by another nitrogen purging. The mixture was then placed in a Tedlar bag filled with hydrogen and stirred at room temperature for 4 days. After the reaction was complete, the carbon-supported palladium was removed through a membrane filter, and the filtrate was completely concentrated to precipitate crude crystals. The crude crystals were washed by adding isopropanol (240 g) and stirring at room temperature. The filtered crystals were dried to obtain DA-8 (yield: 44.8 g, 79.9 mmol, 82%).

[0178] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 6.65 (d, J = 8.9Hz, 4H), 6.50 (d, J = 8.9Hz, 4H), 4.62 (s, 4H), 4.27 (m, 4H), 4.00 (m, 8H), 2.57 (m, 8H), 1.59 (m, 4H).

[0179] [Synthesis of Additives] AD-3 to AD-7, AD-10, and AD-11 are novel compounds not disclosed in the literature. The products of the additives synthesized in Examples 1 to 8 below were obtained through... 1 Identification was performed using H-NMR analysis. The analytical conditions are described below.

[0180] Device: BRUKER ADVANCE III - 500MHz Determination solvent: deuterated dimethyl sulfoxide (DMSO-d6) Reference material: Tetramethylsilane (TMS) 1 (H δ 0.0ppm) <Example 1: Synthesis of AD-3> NMP (35.0 g) was added to DA-6 (5.00 g, 12.0 mmol), and after nitrogen purging, Ac2O (7.35 g, 72.0 mmol) dissolved in NMP (10.0 g) was added. The mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After the reaction was complete, the solution was slowly added dropwise to methanol (300 g) to recrystallize the solution, thus obtaining crude crystals. The crude crystals were dispersed in methanol (150 g), stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-3 (yield: 4.99 g, 9.96 mmol, 83%).

[0181] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 9.76 (s, 2H), 7.46 (d, J = 8.6Hz, 4H), 6.87 (d, J = 8. 6Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.23 (t, 4H), 2.00 (s, 6H), 1.54 (m, 4H).

[0182] <Example 2: Synthesis of AD-4> NMP (8.50 g) was added to DA-6 (1.50 g, 3.60 mmol), and after nitrogen purging, SAH (1.08 g, 10.8 mmol) dissolved in NMP (5.0 g) was added. The mixture was stirred at room temperature for one day to allow the reaction to proceed. After the reaction was complete, the solution was slowly added dropwise to methanol (300 g) to recrystallize the solution, thus obtaining crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-4 (yield: 1.42 g, 2.30 mmol, 64% yield).

[0183] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 12.1 (br, 2H), 9.80 (s, 2H), 7.48 (d, J = 9.1Hz, 4H), 6.87 ( d, J=9.1Hz, 4H), 4.31 (t, 4H), 4.12 (t, 4H), 2.51 (m, 8H), 2.33 (t, 4H), 1.54 (m, 4H).

[0184] <Example 3: Synthesis of AD-5> Under a nitrogen atmosphere, DA-6 (3.33 g, 8.00 mmol), Boc₂O (3.50 g, 16.0 mmol), and THF (33 g) were added to a 100 mL four-necked flask, and the mixture was stirred at room temperature to allow the reaction to proceed. After the reaction was complete, the solvent was removed by evaporation, and 30 g of isopropanol was added. The precipitated solid was filtered off and dried to obtain AD-5 (3.50 g, 5.67 mmol, 71% yield, pinkish-white crystals).

[0185] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 9.11 (s, 2H), 7.32 (d, 4H), 6.83 (d, 4H), 4.30 (t, 4H), 4.10 (t, 4H), 2, 32 (s, 4H), 1.54 (s, 4H), 1.46 (s, 18H).

[0186] <Example 4: Synthesis of AD-6> THF (18.4 g) was added to DA-8 (3.60 g, 6.42 mmol), and after nitrogen purging, Boc2O (8.41 g, 38.5 mmol) dissolved in THF (8.0 g) was added. The mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After the reaction was complete, methanol (3.70 g) was added, and the mixture was stirred at 60 °C for 1 hour. The solvent was removed by evaporation, and the precipitated solid was dispersed in methanol (150 g) and stirred for 30 minutes. The crystals were then filtered off. The obtained crystals were dried to obtain AD-6 (yield: 3.57 g, 4.69 mmol, 73%).

[0187] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 9.12 (s, 2H), 7.34 (d, J = 8.5Hz, 4H), 6.84 (d, J = 9.1Hz, 4H) ), 4.31 (t, 4H), 4.10 (t, 4H), 4.00 (t, 4H), 2.57 (m, 8H), 1.57 (m, 4H), 1.46 (s, 18H).

[0188] <Example 5: Synthesis of AD-7> THF (16 g) was added to DA-7 (2.00 g, 5.20 mmol), and after nitrogen purging, Boc2O (2.62 g, 12.0 mmol) dissolved in THF (4 g) was added. The mixture was stirred at room temperature for 2 days to allow the reaction to proceed. After the reaction was complete, water (100 g) was added in an ice bath to precipitate crystals. The solid obtained by filtration was dried to obtain crude crystals. Methanol (50 g) was added to the crude crystals, and the mixture was heated and stirred at 70 °C. After cooling at room temperature, recrystallization was performed. The crystals obtained by filtration were dried to obtain AD-7 (yield: 2.12 g, 3.62 mmol, 70% yield).

[0189] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 9.23 (s, 2H), 7.37 (d, J = 8.5Hz, 4H), 7.11 (d, J = 8.5Hz, 4H), 4.17 (t, 4H), 2.79 (t, 4H), 2.23 (m, 4H), 1.46 (m, 22H).

[0190] <Example 6: Synthesis of AD-8> THF (20.4 g) was added to DA-5 (3.60 g, 18.0 mmol), and after nitrogen purging, Boc2O (8.24 g, 37.8 mmol) dissolved in THF (6.0 g) was added. The mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After the reaction was complete, methanol (3.63 g) was added, and the mixture was stirred at 60 °C for 1 hour. The solvent was removed by evaporation, and the precipitated solid was dispersed in toluene (150 g) and stirred for 30 minutes. The crystals were then filtered off. The obtained crystals were dried to obtain AD-8 (yield: 5.54 g, 13.9 mmol, 77% yield).

[0191] In DMSO-d6 1 H-NMR (500MHz): δ (ppm) = 9.02 (s, 2H), 7.70 (s, 1H), 7.26 (d, J = 8.1Hz, 4H), 6.89 (d, J = 8.9Hz, 4H), 1.46 (s, 18H).

[0192] <Example 7: Synthesis of AD-10> 4-(benzyloxy)phenol (16.0 g, 80.0 mmol), sodium hydroxide (32 g, 800 mmol), and pure water (288 g) were added, and the mixture was heated to 80 °C. 2-chloroethanol (64.4 g, 800.0 mmol) was slowly added dropwise using a dropping funnel. After the addition was complete, the mixture was stirred at 80 °C for 3 hours. After confirming the reaction was complete by NMR, ethyl acetate (960 g) was added to extract the organic layer, which was then washed separately with saturated sodium chloride aqueous solution (320 g) and pure water (320 g). The extracted organic layer was concentrated, and heptane (160 g) was added for slurry washing. The precipitated crystals were filtered off, washed with heptane, and dried under reduced pressure at 40 °C to obtain powdered crystals (AD-10-1) (yield: 18.7 g, 76.5 mmol, 95% yield, white crystals).

[0193] THF (218 g), 4-dimethylaminopyridine (DMAP, 0.710 g, 5.81 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC•HCl, 26.8 g, 139.6 mmol) were added to the obtained AD-10-1 (14.6 g, 59.6 mmol) and stirred at room temperature for 10 minutes. Then, adipic acid (4.24 g, 29.1 mmol) was added, and the mixture was stirred overnight at room temperature (25 °C). Then, pure water (600 g) was added for crystallization. The resulting crystals were filtered off, washed with pure water and methanol, and dried under reduced pressure at 40 °C to obtain powdered crystals (AD-10-2) (yield: 15.4 g, 25.6 mmol, 88% yield, white crystals).

[0194] THF (154 g) was added to the obtained AD-10-2 (15.4 g, 25.6 mmol), and after nitrogen purging, carbon-supported palladium (5% by mass Pd carbon powder (50% aqueous content) K type, manufactured by NEChemcat) (1.54 g) was added. Nitrogen purging was performed again, and a hydrogen Tedra sampling bag was installed. The mixture was stirred at room temperature (23 °C) for 21 hours. After the reaction was complete, the catalyst was filtered, and the mixture was concentrated. Heptane (90 g) was added, and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were filtered under reduced pressure, and the filter cake was washed with heptane and methanol. The mixture was then dried under reduced pressure at 40 °C to obtain powdered crystals (AD-10) (yield: 10.3 g, 24.6 mmol, 96% yield, white crystals).

[0195] In DMSO-d6 1H-NMR (500MHz): 8.93 (2H, s), 6.73 (4H, d), 6.57 (4H, d), 4.27 (4H, t), 4.04 (4H, t), 2.32 (4H, t), 1.53 (4H, q).

[0196] <Example 8: Synthesis of AD-11> 4-Dimethylaminopyridine (DMAP, 0.015 g, 0.12 mmol) and THF (10 g) were added to AD-10 (1.0 g, 2.39 mmol), and the mixture was stirred at room temperature. Then, a solution of di-tert-butyl dicarbonate (Boc₂O, 1.15 g, 5.3 mmol) dissolved in THF (5.0 g) was added dropwise, and the mixture was reacted at room temperature for 2 hours. After the reaction, the mixture was concentrated by adding IPA (10 g), and the mixture was stirred at room temperature for 30 minutes. The precipitated crystals were filtered under reduced pressure, the filter cake was washed with IPA, and then dried under reduced pressure at 40 °C to obtain powdered crystals (AD-11) (yield: 1.3 g, 2.0 mmol, 86% yield, white crystals).

[0197] In DMSO-d6 1 H-NMR (500MHz): 7.10 (4H, d), 6.95 (4H, d), 4.32 (4H, t), 4.16 (4H, t), 2.32 (4H, t), 1.53 (4H, q), 1.47 (18H, s).

[0198] [Polymer Synthesis] <Synthesis example 1> DA-1 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Then, CA-1 (1.69 g, 7.54 mmol) and NMP (12.4 g) were added, and the mixture was stirred at 40 °C for 18 hours to obtain a 12% by mass solution of polyamic acid (A-1) (viscosity: 225 mPa•s). The polyamic acid had a Mn of 10382 and a Mw of 32874.

[0199] <Synthesis example 2> DA-2 (0.977 g, 4.00 mmol), DA-5 (0.797 g, 4.00 mmol), and NMP (10.1 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while adding nitrogen. Then, 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. 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, thus obtaining a 15% by mass solution of polyamic acid (A-2) (viscosity: 304 mPa•s). The Mn of this polyamic acid was 9284, and the Mw was 26834.

[0200] <Synthesis Example 3> DA-1 (9.74 g, 34.0 mmol), DA-3 (1.37 g, 4.01 mmol), DA-4 (1.11 g, 1.99 mmol), and NMP (106 g) were added to a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Then, CA-1 (7.89 g, 35.2 mmol) and NMP (41.0 g) were added, and the mixture was stirred at room temperature for 18 hours to obtain a 12% by mass solution of polyamic acid (A-3) (viscosity: 210 mPa•s). The Mn of this polyamic acid is 10521, and the Mw is 32302.

[0201] <Synthesis example 4> DA-5 (10.2 g, 51.0 mmol), DA-2 (8.31 g, 34.0 mmol), and NMP (135 g) were added to a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while adding nitrogen. Then, CA-2 (13.8 g, 55.2 mmol) and NMP (47.6 g) were added, and the mixture was stirred at 50 °C for 5 hours. After cooling to room temperature, CA-3 (7.45 g, 25.3 mmol) and NMP (41.1 g) were added, and the mixture was stirred at 70 °C for 18 hours, thus obtaining a 15% by mass solution of polyamic acid (A-4) (viscosity: 309 mPa•s). The Mn of this polyamic acid is 10357, and the Mw is 26452.

[0202] <Synthesis example 5> DA-1 (1.58 g, 5.50 mmol) and NMP (16.8 g) were added to a 50 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Then, CA-4 (1.15 g, 5.28 mmol) and NMP (8.10 g) were added, and the mixture was stirred at 50 °C for 18 hours to obtain a 12% by mass solution of polyamic acid (A-5) (viscosity: 239 mPa•s). The polyamic acid had a Mn of 10094 and a Mw of 33198.

[0203] Table 1 shows the types and amounts of tetracarboxylic acid and diamine components used in the above synthetic examples 1 to 5. It should be noted that in Table 1, the values ​​of tetracarboxylic acid and diamine components represent the proportion (molar parts) of each compound used relative to 100 molar parts of the total amount of diamine components used in the synthesis of each polyamic acid. <Synthesis Example 6> SAH 0.11 g (1.13 mmol) was added to the above polyamic acid solution A-3 (20 g), and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (A-6) with a non-amino-terminated structure.

[0204] [Preparation of liquid crystal alignment agent] <Example 1> A solution of polyamic acid (A-1) obtained in Synthesis Example 1 (A-1) (3.90 g), NMP (0.90 g), GBL (6.36 g), BCS (6.00 g), AD-1 (1% GBL solution, 0.78 g), AD-2 (10% NMP solution, 0.39 g), and AD-3 (0.04 g) obtained in Synthesis Example 2 were added to a solution of polyamic acid (A-2) obtained in Synthesis Example 2 (1.63 g). The mixture was stirred at room temperature for 2 hours to obtain the liquid crystal alignment agent (AL-1) of the present invention.

[0205] <Examples 2-10 and Comparative Examples 1-4> As shown in Table 2, the types and amounts of polymer solutions, solvents and additives used were changed. Otherwise, the same operation as in Example 1 was carried out, thereby obtaining the liquid crystal alignment agents (AL-2) to (AL-10) of Examples 2 to 10 of the present invention and the liquid crystal alignment agents (AL-C1) to (AL-C4) of Comparative Examples 1 to 4. In Table 2, the values ​​for Polymer 1, Polymer 2, Additive 1, Additive 2, Specific Additive, and Other Additives represent the proportion (parts by mass) of each polymer solid component and additive relative to a total of 100 parts by mass of the polymer components.

[0206] [Making of LCD Cells] <Fabrication of ECB-type LCD Cells> A liquid crystal cell with an ECB mode liquid crystal display element was manufactured.

[0207] First, prepare a substrate with electrodes. The substrate is a 30mm × 40mm glass substrate with a thickness of 0.7mm. ITO electrodes with a film thickness of 35nm are formed on the substrate. The electrodes are made of a striped pattern with a spacing of 40mm in length and 10mm in width.

[0208] Next, after filtering the liquid crystal alignment agent obtained above through a filter with a pore size of 1.0 μm, it was spin-coated onto the electrode-bearing substrate prepared above. Then, it was dried on a heating plate at 80°C for 2 minutes, followed by firing in an infrared furnace at 230°C for 20 minutes to form a coating film with a thickness of 60 nm. The liquid crystal alignment film was then rubbed with rayon cloth (Hyperflex, HY-5318) (roller diameter: 120 mm, roller speed: 1000 rpm, moving speed: 20 mm / sec, pressing length: 0.4 mm). Afterwards, it was ultrasonically cleaned in pure water for 1 minute, water droplets were removed by blowing air, and it was dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with liquid crystal alignment films were prepared. On one substrate, spherical spacers with a particle size of 4 μm were dispersed on the surface of the liquid crystal alignment film. A liquid crystal injection port was left, and a sealant (Mitsui Chemicals XN-1500T) was printed around it. The other substrate was then bonded together with the friction direction opposite and the film surfaces facing each other. Afterward, a heat treatment at 150°C for 60 minutes was performed to cure the sealant, creating a blank cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into the blank cell using a reduced-pressure injection method, and the injection port was sealed to obtain the liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and placed at 23°C overnight for evaluation.

[0209] <Fabrication of FFS-driven LCD cell> A liquid crystal cell with an FFS mode liquid crystal display element was manufactured.

[0210] First, a substrate with electrodes is prepared. The substrate is a rectangular glass substrate measuring 30mm × 50mm with a thickness of 0.7mm. An ITO electrode with a full-surface pattern, constituting a common electrode, is formed on the substrate as the first layer. A SiN (silicon nitride) film, formed by CVD (chemical vapor deposition), is formed on the first common electrode as the second layer. The second SiN film has a thickness of 300nm, which functions as an interlayer insulating film. A comb-shaped pixel electrode, formed by patterning the ITO film, is disposed on the second SiN film as the third layer, forming two pixels: a first pixel and a second pixel. Each pixel has dimensions of 10mm in length and 5mm in width. This substrate with electrodes has a structure where the first common electrode and the third pixel electrode are insulated from each other by the second SiN film.

[0211] The third-layer pixel electrode has a comb-like shape formed by multiple electrode lines with a width of 3μm arranged in parallel at 6μm intervals, which are bent at an inner angle of 160° in the central part. A pixel is formed by multiple electrode lines, and has a first region and a second region with the line connecting the bent part as the boundary.

[0212] Next, the liquid crystal alignment agent obtained above was filtered using a 1.0 μm pore size filter and then coated onto the electrode substrate (hereinafter referred to as the "electrode substrate") and a glass substrate with an ITO film formed on the back side and columnar spacers with a height of 4 μm (hereinafter referred to as the "opposite substrate") by spin coating. After drying on a heating plate at 80°C for 2 minutes, it was fired in a hot air circulating oven at 230°C for 20 minutes to form a coating with a thickness of 60 nm. The coating was then rubbed with rayon cloth (Hyperflex, HY-5318) for alignment (roller diameter: 120 mm, roller speed: 1000 rpm, moving speed: 20 mm / sec, pressing length: 0.4 mm). Then, it was cleaned by ultrasonic irradiation in pure water for 1 minute, and after removing water droplets with a blower, it was dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. It should be noted that, regarding the liquid crystal alignment film formed on the aforementioned electrode substrate, the alignment process was performed such that the direction in which the inner angles of the pixel bends are equally divided is parallel to the alignment direction of the liquid crystal. Regarding the liquid crystal alignment film formed on the opposing substrate, the alignment process was performed such that the alignment direction of the liquid crystal on the electrode substrate is consistent with the alignment direction of the liquid crystal on the opposing substrate during the fabrication of the liquid crystal cell. Using the two substrates as a group, a sealant (Mitsui Chemicals XN-1500T) was printed onto the substrates using a dispensing machine. The other substrate was then bonded together with its respective liquid crystal alignment film aligned at 0° and facing each other. The bonded substrates were then pressed together and heated in a hot air circulating oven at 150°C for 60 minutes to cure the sealant, thus producing an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into the empty cell using a depressurized injection method, and the injection port was sealed, thereby obtaining an FFS-driven liquid crystal cell. The obtained liquid crystal cell was then heated at 120°C for 1 hour and placed at 23°C for one night before evaluation.

[0213] [Characteristics Evaluation of LCD Cells] The characteristics of the ECB-type liquid crystal cell and the FFS-driven liquid crystal cell fabricated above are evaluated as follows.

[0214] <Evaluation of Charge Accumulation Based on AC Drive> The FFS-driven liquid crystal cell fabricated above was placed between two polarizing plates arranged orthogonally to each other. With the pixel electrode and the common electrode short-circuited to achieve the same potential, an LED backlight was first irradiated from below the two polarizing plates. The angle of the liquid crystal cell was adjusted to minimize the brightness of the LED backlight transmitted light measured above the two polarizing plates. Next, while applying an AC voltage with a frequency of 60 Hz to the liquid crystal cell, the V-T curve (voltage-transmittance curve) was measured, and the AC voltage with a relative transmittance of 23% was calculated as the driving voltage.

[0215] In the image retention evaluation, an AC voltage of 60 Hz with a relative transmittance of 100% was applied to drive the liquid crystal cell for 60 minutes. Then, an AC voltage with a relative transmittance of 23% was applied, and while scanning the DC voltage, the applied voltage that minimized display flicker was measured. The absolute value of this applied voltage that minimized display flicker was taken as the charge accumulation amount. A lower charge accumulation amount is better.

[0216] It should be noted that the image retention evaluation according to the above method is performed under the temperature condition that the liquid crystal cell temperature is 45°C.

[0217] <Evaluation of Voltage Retention Rate after Backlight Tolerance Test> The above-mentioned ECB type liquid crystal cell is placed under a high-brightness backlight with a surface temperature of 50°C (light source: LED, brightness: 30000 cd / m²). 2 The cells were placed under irradiation for 96 hours. Then, a voltage of 1V was applied to the liquid crystal cell at 60°C for 60μsec, and the voltage was measured after 167ms. The degree to which the voltage was maintained was calculated as the voltage retention rate. A higher voltage retention rate is better.

[0218] [Evaluation of Coating Properties] The liquid crystal alignment agent obtained above was coated onto an ITO substrate measuring 100mm × 100mm with a thickness of 1.1mm using a spin-coating method. After drying on a hot plate at 80°C for 2 minutes, it was fired in a hot air circulating oven at 230°C for 20 minutes to obtain a substrate with a liquid crystal alignment film with a thickness of 60nm. When the substrate with the liquid crystal alignment film is observed with the naked eye, if the coating surface is a uniform surface without any unevenness, it is classified as "good"; if unevenness can be visually confirmed on the coating surface, it is classified as "bad".

[0219] Table 3 shows the evaluation results of charge accumulation, voltage retention rate and coatability of each liquid crystal alignment agent used in Examples 1 to 10 and Comparative Examples 1 to 4.

[0220] It should be noted that the values ​​in parentheses for polymer components and additives represent the proportions (parts by mass) of each polymer solid component and additive, assuming the total content of polymer solid components is set to 100 parts by mass. As shown in Table 3, the liquid crystal alignment film obtained by using a liquid crystal alignment agent with a specific diamine and adding a specific additive as an additive has better charge accumulation, voltage retention and coating properties than the liquid crystal alignment film obtained by using a liquid crystal alignment agent with a specific diamine and without adding any specific additive or other additives (comparison of Examples 1-5 and Examples 8-10 with Comparative Example 1, and Comparison of Examples 6 and Examples 7 with Comparative Example 4).

[0221] On the other hand, when a specific diamine is used and other additives are added as additives, compared with the liquid crystal alignment film obtained by using a specific diamine and without adding specific additives or other additives, one of the following is improved: charge accumulation, voltage retention rate, and coatability, but not all are good (comparison between Comparative Examples 2-3 and Comparative Example 1).

[0222] Industrial availability The liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be applied to various liquid crystal display elements, including those using IPS driving and FFS driving methods. Furthermore, these display elements are not limited to liquid crystal displays for display purposes, but can also be used for liquid crystal alignment films for retardation films; liquid crystal alignment films for scanning antennas and liquid crystal array antennas; or liquid crystal alignment films for transmission-scattering type liquid crystal dimming elements, or for other applications, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials.

[0223] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-052144, filed on March 27, 2024, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. A liquid crystal alignment agent, characterized in that, It contains polymers A and B as components. Polymer A: A polymer selected from the group consisting of a polyimide precursor having structural units derived from tetracarboxylic acid derivatives and structural units derived from diamines, and an imidized polymer of an imidized product of said polyimide precursor, and wherein the structural unit derived from a tetracarboxylic acid derivative comprises the following formula (1T) a The structural unit a-1Ta shown in the figure, as a structural unit derived from diamine, contains the following formula (1D) a The structural unit a-1Da is shown in the diagram. Formula (1T) a In ), X a The symbol indicates a tetravalent organic group, where each R independently represents a hydrogen atom or a monovalent organic group. Formula (1D) a ), Y a The divalent organic group represented by -Ar-L0-Ar'- is indicated; Ar and Ar' each independently represent a benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle, and any hydrogen atom on the ring of Ar and Ar' can be optionally replaced by a monovalent group; Z can independently represent a hydrogen atom or a monovalent organic group; L0 indicates a single bond, or -L a -A-L a’ -; L a L a’ Each can independently represent a single bond, -O-, -S-, -C(=O)-, -O-C(=O)-, -C(=O)-NR-, or -NR-C(=O)-, where R represents a hydrogen atom or a monovalent organic group; A represents a divalent organic group with 1 to 10 carbon atoms having an alkylene structure; Among them, in L a and L a’ In the case of -O-, A does not have -C (=O)- or -O-C (=O)-; Component B: Compound B as shown in formula (1) below; In equation (1), Ar1 and Ar 1’ Each of the above independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, wherein one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring are optionally substituted by a monovalent group, wherein the monovalent group does not include (q1) to (q4). X is a divalent organic group as shown in the following formula (2); *-X1-(Y1-L) ) n -Y2-X2-* (2) ) In equation (2), X1 and X2 independently represent single bonds, -O-, and *1-O-CO-*2, respectively. In *1-O-CO-*2, *1 and *2 represent bonded bonds, and *1 is bonded to Ar1 or Ar. 1’ Bonding; L represents a single bond, -O-, -O-C(=O)-, or -C(=O)-O-. In the presence of multiple Ls, the multiple Ls may be the same or different from each other, wherein at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer from 1 to 6; Y1 and Y2 each independently represent a divalent hydrocarbon group having 1 to 6 carbon atoms, wherein a portion of the hydrogen atoms in the divalent hydrocarbon group is optionally replaced by a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group, and in the presence of multiple Y1s, the multiple Y1s are optionally the same as or different from each other. * indicates that it is related to Ar1 or Ar 1’ The bond of the bond; Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4) and maleimide group. It should be noted that when there are multiple (q1) to (q4) in formula (1), the multiple R1 to R4 may be the same or different from each other. In formula (q1), R1 represents a monovalent organic group, which is derived from a carbonyl group, a sulfonyl group, and *1-C(R) group. q1 Any linking group in )2-*2 is bonded to a nitrogen atom; R2 represents a hydrogen atom or a monovalent organic group; *1-C(R) q1 In )2-*2, *1 represents the bond with a nitrogen atom, and multiple R q1 Each can independently represent a hydrogen atom or a monovalent organic group; *1-CR q1 The *2 in -*2 is bonded to a monovalent organic group containing a heteroatom group; In formula (q2), R3 represents a hydrogen atom or a monovalent organic group; In formula (q3), R4 represents a hydrogen atom, a hydroxyl group, a halogen atom, or a monovalent organic group; In formula (q4), R5 represents a hydrogen atom, a hydroxyl group, or a monovalent organic group.

2. The liquid crystal alignment agent according to claim 1, wherein, The compound B is at least one compound selected from the group consisting of (q1-1) to (q1-5), (q2-1) to (q2-3), (q3-1) to (q3-3), and (q4-1) to (q4-2). 。 3. The liquid crystal alignment agent according to claim 1, wherein, The content of compound B is 0.1 to 50 parts by mass relative to 100 parts by mass of polymer A.

4. A method for manufacturing a liquid crystal alignment film, wherein, The liquid crystal alignment agent as described in any one of claims 1 to 3 is coated onto a substrate, fired, and the resulting film is then subjected to an alignment treatment.

5. A liquid crystal alignment film formed from a liquid crystal alignment agent as described in any one of claims 1 to 3.

6. A liquid crystal display element comprising the liquid crystal alignment film as described in claim 5.

7. The liquid crystal display element according to claim 6, wherein, The liquid crystal display element is driven by either IPS or FFS.

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