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

Abstract

The present application provides 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, the liquid crystal alignment agent being capable of obtaining a liquid crystal alignment film capable of obtaining a low pretilt angle and capable of suppressing AC image sticking. A liquid crystal alignment agent containing the following (A) component and (B) component. (A) component: a polymer (A) having a capability of aligning liquid crystals. (B) component: a compound (B) represented by the following formula (1). (In formula (1), Ar1 and Ar 1’ Each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring being optionally substituted with a monovalent group (excluding (q1) to (q4)). X is a divalent organic group represented by the following formula (2). *-X1-(Y1-L n -Y2-X2-* (2) (In formula (2), X1, X2 each independently represents a single bond, -O-, *1-O-CO-*2 (*1, *2 represent a bonding bond, *1 and Ar 1’ bond). L represents a single bond, -O-, -O-C(=O)-, or -C(=O)-O-, in the case where a plurality of L is present, the plurality of L is optionally the same as or different from each other. Among them, at least one L represents -O-C(=O)- or -C(=O)-O-. n is an integer of 1 to 6. Y1, Y2 each independently represents a divalent hydrocarbon group having a carbon number of 1 to 6, a part of hydrogen atoms of the divalent hydrocarbon group being optionally substituted with a halogen atom, a methyl group, a trifluoromethyl group, or a hydroxyl group. In the case where a plurality of Y1 is present, the plurality of Y1 is optionally the same as or different from each other. * represents a bonding bond with Ar1 or Ar 1’ ). Q, Q' each independently represents a hydrogen atom or a monovalent group selected from the group consisting of (q1) to (q4). Note that, in the case where a plurality of (q1) to (q4) is present in formula (1), the plurality of R1 to R4 is optionally the same as or different from each other. (In formula (q1), R1 represents a monovalent organic group, the monovalent organic group being bonded to a nitrogen atom via any of a carbonyl group, a sulfonyl group, and *1-C(R q1 )2-*2. R2 represents a hydrogen atom or a monovalent organic group. *1 in *1-C(R q1 )2-*2 represents a bonding bond with the nitrogen atom, and a plurality of R q1 each independently represents a hydrogen atom or a monovalent organic group. *2 in *1-C(R q1 )2-*2 is bonded to a monovalent organic group having a heteroatom-containing 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. * represents a bonding bond with Ar1 or Ar 1’ ).

Description

Technical Field

[0001] This 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 thin film transistors (TFTs) that convert electrical signals supplied to the pixel electrodes; etc.

[0005] For liquid crystal alignment films used in liquid crystal display elements represented by IPS and FFS methods, a low pretilt angle is sometimes required from the viewpoint of improving viewing angle characteristics. In addition, for liquid crystal alignment films used in liquid crystal display elements of this type, a high alignment control force is sometimes required to suppress image retention (hereinafter also referred to as AC image retention) caused by long-term AC driving.

[0006] Based on 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 can obtain a liquid crystal alignment film that can achieve a low pretilt angle and suppress AC image retention.

[0007] Solution for solving the problem In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that by using a specific compound, the above-mentioned technical problems could be solved, thereby completing the present invention.

[0008] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, a liquid crystal display element having the liquid crystal alignment film, and a novel compound for the liquid crystal alignment agent, wherein the liquid crystal alignment agent is characterized by containing the following components (A) and (B).

[0009] (A) Component: Polymer (A) with the ability to orient liquid crystals.

[0010] (B) Component: Compound (B) as shown in formula (1) below. (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).

[0011] *-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’ (Bond). L represents a single bond, -O-, -O-C(=O)-, or -C(=O)-O-. In the presence of multiple Ls, the multiple Ls may optionally 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 with 1 to 6 carbon atoms, wherein a portion of the hydrogen atoms of the divalent hydrocarbon group is optionally replaced by a halogen atom, methyl, trifluoromethyl, or hydroxyl. 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 groups. It should be noted that in the presence of multiple (q1) to (q4) groups 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) q1Any 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-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, hydroxyl group, halogen atom, or a monovalent organic group. In formula (q4), R5 represents a hydrogen atom, hydroxyl group, or a monovalent organic group. * indicates a bond with Ar1 or Ar. 1’ (The bond of a bond.) It should be noted that in this specification, * denotes a bond in any case. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Preferred protecting groups for urethane esters include tert-butoxycarbonyl and 9-fluorenylmethoxycarbonyl.

[0012] Invention Effects According to the present invention, a liquid crystal alignment agent capable of producing a liquid crystal alignment film with a low pretilt angle and capable of suppressing AC image retention, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film can be obtained.

[0013] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but the following can be considered as one of the reasons.

[0014] First, compound (B) has alkylene chains and ester bonds in its structure, thus exhibiting high flexibility and plasticity. It can be assumed that the presence of compound (B) near polymer (A), or the introduction of compound (B) into the structure of polymer (A), improves the overall stretchability of the alignment film during alignment treatment, resulting in high liquid crystal alignment and thus achieving the aforementioned effect. Detailed Implementation

[0015] <(A) Ingredient> The liquid crystal alignment agent of the present invention, like known liquid crystal alignment agents, contains polymer (A), which is a polymer capable of aligning liquid crystals. The polymer is not particularly limited as long as it possesses the ability to align liquid crystals. The liquid crystal alignment agent of the present invention may contain one or more of the polymers described above.

[0016] Examples of polymers (A) include: polyimide precursors, polyimides that are imide derivatives of polyimide precursors, acrylic polymers, methacrylic polymers (hereinafter, acrylic polymers and methacrylic polymers are collectively referred to as "(meth)acrylic polymers"), acrylamide polymers, methacrylamide polymers (hereinafter, acrylamide polymers and methacrylamide polymers are collectively referred to as "(meth)acrylic polymers"), polystyrene, polysiloxanes, polyamides, polyesters, polyurethanes, polycarbonates, polyureas, polyphenols (phenolic varnish resins), maleimide polymers, and polymers incorporating compounds having an isocyanuric acid backbone or a triazine backbone.

[0017] The following substances can be listed as raw materials used to manufacture these polymers.

[0018] When the polymer is a polyimide precursor such as polyamic acid or polyamic acid ester, or a polyimide, at least one tetracarboxylic dianhydride and a diamine selected from tetracarboxylic acids or their derivatives are used; when the polymer is a (meth)acrylic acid polymer, (meth)acrylic acid or its derivative or (meth)acrylate or its derivative are used; when the polymer is a (meth)acrylamide polymer, (meth)acrylamide or its derivative are used; when the polymer is polystyrene, styrene or its derivative are used; when the polymer is a polysiloxane, a silane compound having a methoxy or ethoxy group are used; when the polymer is a polyamide, at least one dicarboxylic acid component and a diamine component selected from dicarboxylic acids and their derivatives are used; when the polymer is a polyester, at least one dicarboxylic acid component selected from dicarboxylic acids are used. At least one dicarboxylic acid component and a diol component from acids and their derivatives; in the case of a polyurethane polymer, a compound having an isocyanate and a compound having a hydroxyl group; in the case of a polycarbonate polymer, a bisphenol derivative and phosgene or phosgene equivalents (e.g., trichlorophosgene) or diphenylcarbonate; in the case of a polyurea polymer, a diisocyanate derivative and a diamine component; in the case of a polyphenol (phenolic varnish resin), a phenolic compound component and an aldehyde compound component; in the case of a maleimide polymer, a maleimide derivative homopolymer or copolymer with styrene; in the case of a polymer incorporating a compound having an isocyanuric acid backbone or a triazine backbone, a compound having an isocyanuric acid backbone or a triazine backbone.

[0019] <Polyimide polymers> The polymer (A) contained in the liquid crystal alignment agent of the present invention is preferably selected from at least one polymer (hereinafter also referred to as "polyimide polymer") from the group consisting of a polyimide precursor and a polyimide as an imide derivative of a polyimide precursor, from the viewpoint of practicality as a liquid crystal alignment agent, mechanical strength of the coated film and liquid crystal alignment.

[0020] The aforementioned polyimide polymers can be manufactured using known methods. For example, polyamic acid, as a polyimide precursor, is obtained by polymerizing (condensing) a tetracarboxylic acid component composed of a tetracarboxylic dianhydride or its derivative with a diamine component, and polyimide is obtained by imidizing this polyimide precursor. Examples of tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, or tetracarboxylic acid dialkyl ester dihalides.

[0021] <Tetracarboxylic acid component> Polyamic acids that serve as precursors to polyimides include, for example, polyamic acids derived from tetracarboxylic acid components comprising aromatic tetracarboxylic dianhydrides, acyclic aliphatic tetracarboxylic dianhydrides, or alicyclic tetracarboxylic dianhydrides, or their derivatives. The aforementioned tetracarboxylic dianhydrides or their derivatives may be used alone or in combination of two or more.

[0022] Here, aromatic tetracarboxylic dianhydrides are obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to an aromatic ring. Acyclic aliphatic tetracarboxylic dianhydrides are obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. It is not necessary for the structure to consist solely of a chain hydrocarbon; it may also have an alicyclic or aromatic ring structure in a portion thereof.

[0023] Furthermore, alicyclic tetracarboxylic dianhydrides are obtained by 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. Moreover, 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.

[0024] The polyamic acid described above is preferably a polyamic acid obtained by using a tetracarboxylic acid component containing a tetracarboxylic dianhydride or a derivative thereof as shown in formula (2) below. (In equation (2), Z represents a structure selected from the following equations (x-1) to (x-13).) (In the above formula, R) 1 ~R 4 Each can 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, or a phenyl group. R 5 and R 6Each A1 and A2 independently represents a hydrogen atom or a methyl group. j and k are integers of 0 or 1. A1 and A2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group. The two A2 groups may be the same or different. *1 represents a bond bonded to the anhydride group of one group, and *2 represents a bond bonded to the anhydride group of the other group. As a preferred specific example of the tetracarboxylic acid dianhydride or its derivatives shown in the above formula (2), X can be selected from the substances in the above formulas (x-1) to (x-8) and (x-10) to (x-13).

[0025] Among them, the above formula (x-1) is preferably selected from the group consisting of the following formulas (x1-1) to (x1-6). (In the above formula, *1 represents the bond bonded to the anhydride group of one side, and *2 represents the bond bonded to the anhydride group of the other side.) As preferred examples of the above equations (x-12) and (x-13), the following equations (x-14) to (x-29) can be listed. It should be noted that "*" in the equations indicates the bonding position. The amount of tetracarboxylic acid dianhydride or its derivative shown in formula (2) above used relative to 1 mole of the total tetracarboxylic acid component reacting with the diamine component is preferably 60 to 100 mol%, more preferably 80 to 100 mol%, and even more preferably 90 to 100 mol%.

[0026] <Diamine component> The diamine component used to manufacture the polyimide precursor is not particularly limited, but preferably contains at least one diamine selected from the diamines shown in formula (3) and formula (3A) below (hereinafter also referred to as diamine (H)). The diamine component may contain one diamine alone or two or more diamines in combination. In formula (3), Y3 represents the divalent organic group shown in formula (O) below, and in formula (3A), Y 3a This represents a divalent organic group as shown in formula (a) below. Each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In formula (O), Ar represents a divalent benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle. In the presence of multiple Ars, the two Ars may be identical or different, and any hydrogen atom of the aforementioned benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle may be substituted with a monovalent substituent. p is an integer of 0 or 1. Q3 represents -(CH2). n - (n is an integer from 2 to 18) or the above - (CH2) n A group consisting of at least a portion of -CH2- being replaced by any one of -O-, -C(=O)-, or -O-C(=O)-. (In formula (a), the hydrogen atoms on the benzene ring are optionally substituted with halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, fluoroalkyl groups having 1 to 10 carbon atoms, or fluoroalkoxy groups having 1 to 10 carbon atoms. P is an aromatic ring selected from any of the benzene ring or biphenyl structures, and the hydrogen atoms on the benzene ring or biphenyl structure are optionally substituted with methyl or fluorine atoms. n is an integer from 0 to 5. When n is an integer greater than 2, n Ps independently have the above definition.) Substituents for the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle in the above formula (O) can include, for example, halogen atoms, alkyl groups with 1 to 10 carbon atoms, alkenyl groups with 2 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, fluoroalkyl groups with 1 to 10 carbon atoms, fluoroalkenyl groups with 2 to 10 carbon atoms, fluoroalkoxy groups with 1 to 10 carbon atoms, carboxyl groups, hydroxyl groups, alkoxycarbonyl groups with 1 to 10 carbon atoms, cyano groups, nitro groups, etc.

[0027] As a preferred specific example of the aromatic heterocycle in the above formula (O), the aromatic heterocycles exemplified in the nitrogen-containing heterocycles described later can be listed. Among them, pyridine rings, pyrimidine rings, pyrazine rings, benzimidazole rings, or quinoline rings are preferred.

[0028] From the viewpoint of improving liquid crystal orientation, the divalent organic group shown in the above formula (O) is preferably a divalent organic group shown in any of the following formulas (o-1) to (o-12). It should be noted that the hydrogen atoms on the ring in the following formulas (o-1) to (o-10) and (o-12) are optionally replaced by the substituents exemplified in the above diamine (H). (In the formula, X1 and X2 each independently represent a single bond or -O-.) (In equation (o-7), each X7 independently represents a single bond or -O-. When n is 1, at least one of the two X7s represents -O-. In equation (o-12), each of the two m independently has the above definition.) From the viewpoint of improving liquid crystal orientation, the divalent organic group shown in formula (a) of formula (3A) above is preferably the divalent organic group shown in formulas (A-1) to (A-5) below. The total proportion of at least one diamine selected from the diamines shown in formula (3) and formula (3A) relative to 1 mole of diamine component is preferably 1 to 95 mol%, more preferably 1 to 90 mol%, and even more preferably 5 to 90 mol%.

[0029] From the viewpoint of improving the voltage retention rate of the obtained liquid crystal alignment film, the polyimide polymer used in the present invention can have a structure containing at least one nitrogen atom selected from the group consisting of nitrogen-containing heterocycles (excluding the imide rings present in the polyimide), secondary amino groups, and tertiary amino groups (hereinafter also referred to as a specific nitrogen-containing structure). A polyimide polymer having a specific nitrogen-containing structure can be obtained by using a monomer having a nitrogen-containing structure, such as a diamine having a specific nitrogen-containing structure, as a raw material in at least a portion.

[0030] Examples of nitrogen-containing heterocycles that a diamine with a specific nitrogen-containing structure can possess include: pyrrole rings, imidazole rings, pyrazole rings, triazole rings, pyridine rings, pyrimidine rings, pyridazine rings, pyrazine rings, indole rings, benzimidazole rings, purine rings, quinoline rings, isoquinoline rings, naphthidine rings, quinoxaline rings, phthalazine rings, triazine rings, carbazole rings, acridine rings, piperidine rings, piperazine rings, pyrrolidine rings, and hexamethyleneimine rings. Among these, pyridine rings, pyrimidine rings, pyrazine rings, benzimidazole rings, piperidine rings, piperazine rings, quinoline rings, carbazole rings, or acridine rings are preferred.

[0031] The diamines with a specific nitrogen-containing structure described above may have secondary and tertiary amino groups, for example, represented by the following formula (n). In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms. "*1, *2" represent bonds bonded to the hydrocarbon group.

[0032] Examples of the monovalent hydrocarbon group R in formula (n) above include: alkyl groups such as methyl, ethyl, and propyl; cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and methylphenyl. R is preferably a hydrogen atom or a methyl group.

[0033] Specific examples of diamines having a specific nitrogen-containing structure include, in addition to the diamines (H) having an aromatic heterocycle mentioned above, 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, compounds shown in formulas (Dp-1) to (Dp-7) below, and compounds shown in formulas (z-1) to (z-19) below. (X3 and X4 each independently represent a single bond or -(CH2)n- (n is an integer from 1 to 4).) From the viewpoint of improving the voltage retention rate of liquid crystal display elements, the proportion of diamines having a specific nitrogen-containing structure used relative to the total amount of diamines used in synthesis is preferably 1 mol% or more, more preferably 2 mol% or more. Furthermore, this proportion is preferably 90 mol% or less, more preferably 80 mol% or less.

[0034] The polyimide polymers used in this invention may also contain diamines other than those described above (hereinafter also referred to as "other diamines"). Examples of other diamines are listed below, but the invention is not limited to these.

[0035] The molecule contains the group "-N(D)- (D represents a carbamate protecting group)," excluding diamines with 6 to 30 carbon atoms in D; 4,4'-diaminoazobenzene and the following formula (d T -1) ~ (d) T-3) and other diamines having photooriented groups; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminobenzyl)benzene, diamines shown in formulas (3i-1) to (3i-5) below, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the following formula (3 Diamines containing a carboxyl group, such as the diamine compounds shown in formulas (b-1) to (3b-4); 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzoylaniline, 4,4'-diaminoazobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-inden-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine Diamines with urea bonds, such as those represented by formulas (h-1) to (h-3); diamines with amide bonds, such as those represented by formulas (h-4) to (h-6); diamines with photopolymerizable groups at the ends, such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallyl aniline; cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, and cholesteryl 3,5-diaminobenzoate. Diamines having a steroidal skeleton, such as 3,5-diaminobenzoic acid lanosteryl ester and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by formulas (V-1) to (V-6) below; diamines having a siloxane bond, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; diamines having an oxazoline ring structure, such as formulas (Ox-1) to (Ox-2) below; and diamines formed by bonding two amino groups to any group represented by formulas (Y-1) to (Y-167) as described in International Publication No. 2018 / 117239. (In equations (3i-1) to (3i-3), the two n can be chosen to be the same or different.) (In equation (3b-1), A) 1The following symbols represent single bonds: -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-. m1 and m2 each independently represent integers from 0 to 4, and m1 + m2 represents integers from 1 to 4. In equation (3b-2), m3 and m4 each independently represent integers from 1 to 5. In equation (3b-3), A... 2 m5 represents a straight-chain or branched alkyl group with 1 to 5 carbon atoms, where m5 represents an integer from 1 to 5. In formula (3b-4), A 3 and A 4 Each of these characters independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, where m6 represents an integer from 1 to 4. (In the above formulas (V-1) to (V-6), X) v1 ~X v4 X p1 ~X p2 Each can be represented independently as – (CH2) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2OCO-, -COO- or -OCO-, X v5 This represents -O-, -CH2O-, -CH2OCO-, -COO-, or -OCO-. X a Represents single bonds, -O-, -NH-, -O- (CH2). m -O-, -C(CH3)2-, -CO-, -(CH2) m -, -SO2-, -O-C(CH3)2-, -CO-(CH2) m -, -NH-(CH2) m -, -SO2-(CH2) m -, -CONH- (CH2) m -, -CONH- (CH2) m -NHCO-, -COO- (CH2) m -OCO-, -CONH-, -NH- (CH2)m -NH- or -SO2-(CH2) m -SO2- (where m represents an integer from 1 to 6), R v1 ~R v4 R 1a ~R 1b Each of the following can independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. In formula (V-6), the two k's may optionally be the same or different from each other. As diamines having the intramolecular group "-N(D)-" (where D represents a urethane protecting group) excluding D, and having 6 to 30 carbon atoms, examples include compounds represented by formulas (5-1) to (5-15) and (5-18) to (5-20). (As (5-2), (5-16) to (5-17) are preferably examples.) (Boc represents tert-butoxycarbonyl.) <(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).

[0036] *-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, methyl, trifluoromethyl, or hydroxyl. 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) below. 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-CR) q1 - *2 Any linker in the equation 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 group, halogen atom, or a monovalent organic group. In formula (q4), R5 represents a hydrogen atom, hydroxyl group, or a monovalent organic group. * indicates a bond with Ar1 or Ar. 1’ (The bond of a bond.) Examples of monovalent organic groups in R1 of formula (q1) include: monovalent hydrocarbon groups with 1 to 30 carbon atoms, monovalent groups formed by substituting 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 R6 is independently a hydrogen atom or a monovalent organic group with 1 to 6 carbon atoms), and -SO2-, etc. 1b ), the above monovalent hydrocarbon group or the above monovalent group (R) 1b A monovalent group having a heterocyclic structure, formed by replacing at least one of the hydrogen atoms bonded to a carbon atom with a substituent (x). Specifically, R1 is a carbonyl group, a sulfonyl group, or *1-C(R... q1 Any linking group in )2-*2 is bonded to a nitrogen atom.

[0037] 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, the methylene group of which is replaced by -O-, -S-, -CO-, -COO-, -COS-, -NR6-, -CO-NR6-, -Si(R6)2- (wherein, in the presence of multiple R6 groups, each R6 is independently a hydrogen atom or a monovalent organic group with 1 to 6 carbon atoms), -SO2-, etc., to form a monovalent group (R b ), the above monovalent hydrocarbon group or the above monovalent group (R) b A monovalent group consisting of a carbon atom and at least one hydrogen atom bonded to the carbon atom is replaced by a substituent (x), or a monovalent group having a heterocyclic ring.

[0038] 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.

[0039] 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 they are not limited to these.

[0040] From the viewpoint of obtaining the appropriate 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] If we list the groups "*-(Y1-L)" in the above formula (2), n A more preferred specific example of “-Y2-*” can be listed below.

[0045] *-(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 structure described, p, q, and r are each an independent integer from 1 to 6.

[0046] 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 groups is 20 or less.

[0047] As a preferred 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 R) C (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) ~ (q1-d). As R O Preferred specific examples may include organic groups formed by removing a hydrogen atom from the hydroxyl group of an alcohol, oxime, or phenol compound.

[0048] As R N Preferred specific examples may include organic groups formed 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.

[0049] As R C Preferred specific examples may include alkyl, alkenyl, organic groups formed by removing a hydrogen atom from a carbon atom of an active methylene compound, or -(CH2). n -COOH (n is an integer from 1 to 6).

[0050] 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, alkyl lactate, and other saturated alcohols; allyl alcohol and other acyclic unsaturated alcohols; and benzyl alcohol, 9-fluorenylmethanol, and other alcohols with aromatic rings.

[0051] Examples of the aforementioned oxime compounds include acetone oxime, formaldehyde oxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and benzophenone oxime.

[0052] Examples of the aforementioned lactam compounds include ε-caprolactam and γ-butyrolactam.

[0053] Examples of the aforementioned phenolic compounds include: phenol, naphthol, cresol, xylenol, and halogenated phenols.

[0054] 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.

[0055] Examples of the aforementioned active methylene compounds include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

[0056] Examples of the aforementioned pyrazole compounds include pyrazole, methylpyrazole, and dimethylpyrazole.

[0057] 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.

[0058] Examples of the aforementioned imide compounds include maleimide, succinimide, phthalimide, and their derivatives.

[0059] Specific examples of preferred R3 in formula (q2) include: hydrogen atom; straight-chain alkyl group having 1 to 6 carbon atoms; alkenyl group having 2 to 6 carbon atoms; carbamate organic groups represented by benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, Boc group, etc.; glycidyl group; epoxycyclohexylmethyl (preferably 2,3-epoxycyclohexylmethyl or 3,4-epoxycyclohexylmethyl); groups 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.) As a preferred specific example of R4 in formula (q3), the following can be listed: hydroxyl group; -OR q3 (R) q3 The group represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, 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); a group having an oxetane ring as shown in the above formula (q2-1).

[0060] As a preferred specific example of R5 in 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.

[0061] Ar1 and Ar replace the above equation (2) 1’ The monovalent groups on the benzene ring, the biphenyl structure, or the hydrogen atom of the naphthalene ring can be listed as: halogen atoms, alkyl groups with 1 to 3 carbon atoms, alkenyl groups with 2 to 3 carbon atoms, cyano groups, nitro groups, etc.

[0062] 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 (q2-2), (q3-1) to (q3-3) and (q4-1) to (q4-2). The preferred content of compound (B) represented by the above formula (1) in the liquid crystal alignment agent of the present invention is 0.1 to 50 parts by mass relative to 100 parts by mass of polymer (A), more preferably 0.1 to 30 parts by mass, and even more preferably 0.1 to 10 parts by mass.

[0063] <Manufacturing methods of polyamic acid and polyimide> The polyamic acid used as a polyimide precursor in this invention can be synthesized, for example, by reacting the above-mentioned tetracarboxylic acid component with the above-mentioned diamine component in the presence of an organic solvent (polymerization).

[0064] For detailed synthesis methods of polyimide precursors and polyimides, please refer to, for example, WO2015 / 012368.

[0065] Regarding the aforementioned polyimide precursor and polyimide, it can be an end-modified polymer obtained by using a suitable end-capping agent together with the tetracarboxylic acid component and diamine as described above during the manufacture of the polyimide precursor and polyimide.

[0066] Examples of end-modifying agents include: acetic anhydride, maleic anhydride, succinic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, and other acid anhydrides; di-tert-butyl dicarbonate; aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, and other monoamine compounds; ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, and other monoisocyanate compounds.

[0067] The proportion of the terminal modifier used relative to the total 100 moles of the diamine components used is preferably 40 moles or less, and more preferably 30 moles or less.

[0068] <Polymer solution viscosity / molecular weight> Regarding the polyamic acid, polyamic acid ester, and polyimide used in this invention, when preparing a solution with a concentration of 10-15% by weight, from an operational point of view, a solution viscosity of 10-1000 mPa·s is preferred, for example, but not particularly limited. It should be noted that the solution viscosity (mPa·s) of the aforementioned polymers is a value measured at 25°C using an E-type rotational viscometer for a polymer solution with a concentration of 10-15% by weight prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0069] The weight-average molecular weight (Mw) of the polyamic acid, polyamic acid ester, and polyimide, as determined by gel permeation chromatography (GPC) based on the polyethylene glycol / polyethylene oxide ratio, is preferably 1,000 to 500,000, more preferably 2,000 to 500,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) of the polyethylene glycol / polyethylene oxide ratio determined by GPC, is preferably 15 or less, more preferably 10 or less. Within this molecular weight range, good liquid crystal alignment of the liquid crystal display element can be ensured.

[0070] <Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention contains the polymer (A) having the ability to align liquid crystals and the compound (B) of the above formula (1). The liquid crystal alignment agent of the present invention preferably has the form in which the compound (B) of the above formula (1) is added to a solution obtained by dissolving the polymer (A) having the ability to align liquid crystals in a solvent.

[0071] The content (concentration) of polymer (A) 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, and from the perspective of the storage stability of the solution, it is preferably 10% by mass or less.

[0072] The solvent used in liquid crystal alignment agents 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-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-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 20-99% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 20-90% by mass, and particularly preferably 30-80% by mass.

[0073] 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 (also known as a poor solvent). Specific examples of the solvents used are described below, but are not limited to these.

[0074] For example, diisopropyl ether, diisobutyl ether, diisobutylmethanol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxyacetic acid butyl ester, 1-methylacetic acid pentyl ester, 2-ethylacetic acid butyl ester, 2-ethylacetic acid hexyl ester, 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 acetate, propylene 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.

[0075] Preferably, the solvents used are 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. The content of the undesirable solvent is preferably 1-80% by mass of the total solvent contained in the liquid crystal alignment agent, more preferably 10-80% by mass, and particularly preferably 20-70% by mass. The type and content of the undesirable solvent are appropriately selected based on the coating apparatus, coating conditions, and coating environment of the liquid crystal alignment agent.

[0076] Preferred solvent combinations for good and bad solvents include: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone and propylene glycol diacetate; N,N-dimethyllactic acid and diisobutyl ketone; N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N N-methyl-2-pyrrolidone with ethylene glycol monobutyl ether acetate; N-ethyl-2-pyrrolidone with dipropylene glycol dimethyl ether; N,N-dimethyl lactamide with ethylene glycol monobutyl ether; N,N-dimethyl lactamide with propylene glycol diacetate; N-ethyl-2-pyrrolidone with diethylene glycol diethyl ether; N,N-dimethyl lactamide with diethylene glycol diethyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl- 2-Pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and 2,6-dimethyl-4-heptanone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and dipropylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and 2,6-dimethyl-4-heptanone; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and propylene glycol diacetate; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and 2,6-dimethyl-4-heptanone. - Heptanone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol; N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol monomethyl ether; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and propylene glycol diacetate; N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether and diisobutyl ketone; N-ethyl-2-pyrrolidone, γ-butyrolactone and diisobutyl ketone;N-ethyl-2-pyrrolidone, N,N-dimethyllactic acid, and diisobutyl ketone, etc.

[0077] The liquid crystal alignment agent of the present invention may also contain, in addition to the polymer (A) and compound (B), components other than solvents (hereinafter also referred to as additive components). Examples of such additive components include: adhesion promoters for improving the adhesion between the liquid crystal alignment film and the substrate, and between the liquid crystal alignment film and the sealant; compounds for improving the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compounds); and dielectric or conductive materials for adjusting the dielectric constant and resistance of the liquid crystal alignment film. The liquid crystal alignment agent of the present invention may contain one or more of the aforementioned additive components.

[0078] From the viewpoint of exhibiting good resistance to AC remnants and significant improvement in film strength, the following compounds can be listed as crosslinking compounds: compounds having at least one group selected from the group consisting of ethylene oxide, oxetane, protected isocyanate group, protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Michaelis acid structure, and a cyclic carbonate group, hydroxyalkylamide compounds, or compounds represented by formula (e) below. (In formula (e), A represents an (m+n) valence organic group having an aromatic ring. m represents an integer from 1 to 6, and n represents an integer from 0 to 4. R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Any hydrogen atom in the above aromatic ring may optionally be substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms. When m is 2 or more, each R independently has the above definition.) Specific examples of compounds containing ethylene oxide include compounds described in paragraph 0037 of Japanese Patent Application Publication No. 10-338880 and compounds with a triazine ring in their skeleton as described in International Patent Publication No. 2017 / 170483, as well as compounds containing two or more ethylene oxide groups. These may include compounds containing nitrogen atoms, such as N,N,N',N'-tetraglycidyl-m-phenylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds shown in formulas (r-1) to (r-3) below. Specific examples of compounds having oxetane groups include compounds having two or more oxetane groups as described in paragraphs 0170 to 0175 of International Publication No. 2011 / 132751.

[0079] Specific examples of compounds having protected isocyanate groups include compounds having two or more protected isocyanate groups as described in paragraphs 0046 to 0047 of Japanese Patent Application Publication No. 2014-224978, and compounds having three or more protected isocyanate groups as described in paragraphs 0119 to 0120 of International Publication No. 2015 / 141598, which can be compounds represented by the formulas (bi-1) to (bi-3) below. As a specific example of a compound having a protected isothiocyanate group, compounds having two or more protected isothiocyanate groups as described in Japanese Patent Application Publication No. 2016-200798 can be cited.

[0080] As a specific example of a compound having a group containing an oxazoline ring structure, the compound containing two or more oxazoline ring structures described in paragraph 0115 of Japanese Patent Application Publication No. 2007-286597 can be cited.

[0081] As a specific example of a compound having a group containing a Michaelis acid structure, compounds having two or more Michaelis acid structures as described in International Publication No. 2012 / 091088 can be cited.

[0082] Specific examples of compounds having cyclic carbonate groups include the compound described in International Publication No. 2011 / 155577.

[0083] Specific examples of hydroxyalkylamide compounds other than those shown in formula (1) above include compounds described in International Publication No. 2015 / 072554, Japanese Patent Application Publication No. 2016-118753, paragraph 0058, Japanese Patent Application Publication No. 2016-200798, and International Publication No. 2019 / 142927, as well as compounds shown in formulas (hd-1) to (hd-8) and formulas (hd1-1) to (hd1-4) below. Examples of (m+n) valence organic groups having aromatic rings in A of formula (e) above include: (m+n) valence aromatic hydrocarbon groups with 6 to 30 carbon atoms; (m+n) valence organic groups formed by direct or via linking groups of aromatic hydrocarbon groups with 6 to 30 carbon atoms; and (m+n) valence groups having aromatic heterocycles. Examples of such aromatic hydrocarbons include benzene and naphthalene. Examples of such aromatic heterocycles include: pyrrole rings, imidazole rings, pyrazole rings, pyridine rings, pyrimidine rings, quinoline rings, isoquinoline rings, carbazole rings, pyridazine rings, pyrazine rings, benzimidazole rings, indole rings, quinoxaline rings, acridine rings, etc. Examples of such linking groups include: alkylene groups with 1 to 10 carbon atoms or groups formed by removing one hydrogen atom from the aforementioned alkylene groups; and divalent or trivalent cyclohexane rings, etc. It should be noted that any hydrogen atom of the aforementioned alkylene group may optionally be replaced by an alkyl group having 1 to 6 carbon atoms, a fluorine atom, or an organic group such as trifluoromethyl. Specific examples include the compounds described in International Publication No. 2010 / 074269 and the compounds shown in formulas (e-1) to (e-10) below. The above-described compounds are examples of cross-linking compounds and are not limited to these. For example, other components not described above may be listed in International Publication No. 2015 / 060357, page 53, paragraph 0105 to page 55, paragraph 0116. Furthermore, two or more cross-linking compounds may be combined.

[0084] The content of the crosslinking compound in the liquid crystal alignment agent of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent. From the viewpoint of promoting crosslinking reaction progress and exhibiting good resistance to AC image retention, it is more preferably 1 to 15 parts by mass.

[0085] 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, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy 3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 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-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxoethylidene)-3-aminopropyltrimethoxysilane, N-bis(oxoethylidene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyl Silane coupling agents include oxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. When using silane coupling agents, from the viewpoint of exhibiting good resistance to AC image retention, the amount of polymer component contained in the liquid crystal alignment agent is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of the polymer component.

[0086] Examples of dielectric or conductive materials used to adjust the dielectric constant and resistance of liquid crystal alignment films include monoamines such as 3-aminomethylpyridine, which have nitrogen-containing aromatic heterocycles.

[0087] <Liquid crystal alignment film / liquid crystal display element> The liquid crystal alignment film of the present invention is formed from the above-described liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used as a liquid crystal alignment film for horizontally aligned or vertically aligned (VA type) liquid crystal display elements, wherein the liquid crystal alignment film of the present invention is suitable for horizontally aligned liquid crystal display elements such as IPS or FFS types. The liquid crystal display element of the present invention includes the above-described liquid crystal alignment film. The liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4) or steps (1) to (2) and (4).

[0088] <Process (1): The process of coating liquid crystal alignment agent> For example, the liquid crystal alignment agent of the present invention is coated onto one side of a substrate having a patterned transparent conductive film using a suitable coating method such as roll coating, spin coating, printing, or inkjet coating. Here, the substrate is not particularly limited as long as it has high transparency; it can also be used in conjunction with glass substrates, silicon nitride substrates, or plastic substrates such as acrylic substrates or polycarbonate substrates. Furthermore, in reflective liquid crystal display elements, if only a single-sided substrate is used, an opaque material such as a silicon wafer can be used, and the electrodes can be made of light-reflecting materials such as aluminum. In addition, when manufacturing IPS or FFS type liquid crystal elements, a substrate having electrodes composed of a patterned comb-shaped transparent conductive film or metal film and an opposing substrate without electrodes are used.

[0089] 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.

[0090] <Process (2): The process of firing the coated liquid crystal alignment agent> 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 by 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. The temperature for removing the solvent from the liquid crystal alignment agent can be, for example, at 40 to 180°C. From the viewpoint of shortening the process, it can be performed at 40 to 150°C. The firing time is not particularly limited, and examples include 1 to 10 minutes or 1 to 5 minutes. In the case of thermal imidization of the amyl acid or amyl ester in the polymer, the firing step can be performed after the above-mentioned organic solvent removal step, for example, at a temperature range of 150 to 300°C or 150 to 250°C. The firing time is not particularly limited, and examples include 5 to 40 minutes or 5 to 30 minutes.

[0091] If the thickness of the film after firing is too thin, the reliability of the liquid crystal display element may be reduced. Therefore, it is preferred to be 5 to 300 nm, and more preferably 10 to 200 nm.

[0092] <Step (3): The step of oriented treatment of the film obtained in step (2)> Step (3) is a step of aligning the film obtained in step (2) as needed. That is, in horizontally aligned liquid crystal display elements such as IPS or FFS, the coating is subjected to an alignment capability imparting treatment. On the other hand, in vertically aligned liquid crystal display elements such as VA or PSA, the formed coating can be used as a liquid crystal alignment film as is, but an alignment capability imparting treatment can also be performed on the coating. As an alignment treatment method for liquid crystal alignment film, the rubbing treatment method and the photo-alignment treatment method are preferred. As a photo-alignment treatment method, the following method can be listed: irradiating the surface of the above-mentioned film with radiation polarized in a fixed direction, and, depending on the situation, preferably performing a heating treatment at a temperature of 150 to 250°C to impart liquid crystal alignment (also known as liquid crystal alignment capability). As radiation, ultraviolet light or visible light with a wavelength of 100 to 800 nm can be used. Among them, ultraviolet light with a wavelength of 100 to 400 nm is preferred, and ultraviolet light with a wavelength of 200 to 400 nm is more preferred.

[0093] The preferred radiation dose is 1–10,000 mJ / cm². 2 More preferably, it is 100–5000 mJ / cm³. 2 Furthermore, in order to improve the alignment of liquid crystals under irradiation, the substrate having the above-described film can be irradiated while being heated at 50–250°C. The liquid crystal alignment film prepared as described above enables the liquid crystal molecules to be stably aligned in a fixed direction.

[0094] Furthermore, in the above methods, water or solvents can also be used to contact the liquid crystal alignment film irradiated with polarized radiation, or the liquid crystal alignment film irradiated with radiation can be heated.

[0095] The solvent used in the above-mentioned contact treatment is not particularly limited as long as it dissolves the decomposition products generated from the film due to radiation irradiation. Specific examples include: water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. Among these, water, 2-propanol, 1-methoxy-2-propanol, or ethyl lactate are preferred from the perspective of versatility and solvent safety. Water, 1-methoxy-2-propanol, or ethyl lactate are more preferred. One solvent or a combination of two or more solvents can be used.

[0096] The heat treatment of the radiation-irradiated coating is preferably performed at 50–300°C for 1–30 minutes, and more preferably at 120–250°C for 1–30 minutes.

[0097] <Process (4): Process of manufacturing LCD cell> Prepare two substrates with liquid crystal alignment films formed thereon as described above, and place liquid crystal between the two substrates arranged opposite each other. Specifically, the following two methods can be listed. In the first method, firstly, place the two substrates opposite each other with a gap (cell gap) between them, with their respective liquid crystal alignment films facing each other. Next, use a sealant to bond the peripheries of the two substrates together, inject a liquid crystal composition into the cell gap defined by the substrate surfaces and the sealant, and after it comes into contact with the film surface, seal the injection hole.

[0098] In addition, a second method is known as the ODF (One Drop Fill) method. For example, an ultraviolet-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 points 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 ultraviolet light to cure the sealant. Regardless of the method 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 alignment during liquid crystal filling.

[0099] It should be noted that when the coating has been rubbed, the two substrates are arranged opposite each other at a specified angle, such as orthogonal or antiparallel, with the rubbing directions of each coating.

[0100] As a sealant, for example, epoxy resin containing a curing agent and alumina spheres as spacers can be used. As a liquid crystal, nematic liquid crystals and smectic liquid crystals can be listed, with nematic liquid crystals being preferred.

[0101] Furthermore, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. Examples of polarizing plates attached to the outer surface of the liquid crystal cell include polarizing plates 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 polarizing plates made of the H film itself.

[0102] The liquid crystal display element of the present invention can be effectively applied to various devices, such as clocks, portable game consoles, word processors, laptops, car navigation systems, portable camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, LCD TVs, information displays, and other display devices. Furthermore, the polymer composition contained in the aforementioned liquid crystal alignment agent can also be used as a liquid crystal alignment film for retardation films; a liquid crystal alignment film for scanning antennas and liquid crystal array antennas; or a liquid crystal alignment film for transmission-scattering type liquid crystal dimming elements; or it can also be used for other applications, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials.

[0103] 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.

[0104] (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-9: These are compounds represented by the formulas (DA-1) to (DA-9) below. (In the above formula, Boc represents tert-butoxycarbonyl.) (additive) AD-1 to AD-11: These are compounds represented by the formulas (AD-1) to (AD-11) below. Of the above-mentioned additives, AD-3 to AD-7, AD-10 and AD-11 are included in the range of specific additives equivalent to compound (B) of this application.

[0105] (In the above formula, Boc represents tert-butoxycarbonyl.) (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.

[0106] <Determination of molecular weight> Using the ambient temperature GPC (gel permeation chromatography) apparatus described below and under the following conditions, the determination was carried out, and Mn and Mw were calculated using the polyethylene glycol / polyethylene oxide conversion value.

[0107] GPC Unit: GPC-101 (manufactured by RESONAC) Chromatographic columns: GPC KD-803, GPC KD-805 (manufactured by RESONAC) in tandem Column temperature: 50℃ Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, anhydrous phosphoric acid (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L) Flow rate: 1.0 mL / min Standard samples used for calibration curve preparation: 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).

[0108] [Synthesis of monomers] DA-9 is a novel compound not disclosed in the literature. The product in the monomer synthesis example 1 below was synthesized by... 1 Identification was performed using 1H-NMR analysis. The analytical conditions are as follows.

[0109] Device: BRUKER ADVANCE III - 500MHz Determination solvent: deuterated dimethyl sulfoxide (DMSO-d6) Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H) <Synthesis Example 1: Synthesis of DA-9> 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 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 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 to recrystallize the crystals. The filtered crystals were dried to obtain DA-9-1 (yield: 60.4 g, 97.2 mmol, 75% yield).

[0110] 1 H-NMR (500MHz) in DMSO-d6: 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).

[0111] The DA-9-1 (60.3 g, 97.2 mmol) obtained above was replaced with THF (1.2 kg) for nitrogen replacement, followed by the addition of carbon-supported palladium (5% Pd carbon powder (containing water), K type, manufactured by NECHEMCAT) (6.0 g), and another nitrogen replacement was performed. The mixture was then placed in a hydrogen-filled Tedlar bag 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-9 (yield: 44.8 g, 79.9 mmol, 82%).

[0112] 1H-NMR (500MHz) in DMSO-d6: 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).

[0113] [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 9 below are obtained through... 1 Identification was performed using 1H-NMR analysis. The analytical conditions are as follows.

[0114] Device: BRUKER ADVANCE III - 500MHz Determination solvent: deuterated dimethyl sulfoxide (DMSO-d6) Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H) <Example 1: Synthesis of AD-3> Nitrogen replacement was performed by adding NMP (35.0 g) to DA-7 (5.00 g, 12.0 mmol), followed by the addition of Ac2O (7.35 g, 72.0 mmol) dissolved in NMP (10.0 g). 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 mixture, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, then filtered off. The resulting crystals were dried to obtain AD-3 (yield: 4.99 g, 9.96 mmol, 83% yield).

[0115] 1 H-NMR(500MHz)in DMSO-d6: 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).

[0116] <Example 2: Synthesis of AD-4> Nitrogen replacement was performed by adding NMP (8.50 g) to DA-7 (1.50 g, 3.60 mmol), followed by the addition of SAH (1.08 g, 10.8 mmol) dissolved in NMP (5.0 g). 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 mixture, yielding crude crystals. The crude crystals were dispersed in methanol (150 g) and stirred for 30 minutes, then filtered off. The resulting crystals were dried to obtain AD-4 (yield: 1.42 g, 2.30 mmol, 64% yield).

[0117] 1 H-NMR(500MHz)in DMSO-d6: 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).

[0118] <Example 3: Synthesis of AD-5> Under a nitrogen atmosphere, DA-7 (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 using an evaporator, 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, powdery white crystals).

[0119] 1 H-NMR (500MHz) in DMSO-d6: 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).

[0120] <Example 4: Synthesis of AD-6> Nitrogen replacement was performed by adding THF (18.4 g) to DA-9 (3.60 g, 6.42 mmol), followed by the addition of Boc₂O (8.41 g, 38.5 mmol) dissolved in THF (8.0 g). 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 then removed using an evaporator, and the precipitated solid was dispersed in methanol (150 g). The mixture was stirred for 30 minutes, and the crystals were filtered off. The resulting crystals were dried to obtain AD-6 (yield: 3.57 g, 4.69 mmol, 73%).

[0121] 1 H-NMR(500MHz)in DMSO-d6: 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).

[0122] <Example 5: Synthesis of AD-7> After nitrogen replacement with 16 g of THF relative to DA-8 (2.00 g, 5.20 mmol), 2.62 g of Boc₂O dissolved in 4 g of THF (12.0 mmol) was added, and the mixture was stirred at room temperature for 2 days to allow the reaction to proceed. After the reaction was complete, 100 g of water was added under ice bath conditions 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, the crystals were recrystallized. The filtered crystals were dried to obtain AD-7 (yield: 2.12 g, 3.62 mmol, 70% yield).

[0123] 1 H-NMR (500MHz) in DMSO-d6: 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).

[0124] <Example 6: Synthesis of AD-8> Nitrogen replacement was performed by adding THF (20.4 g) to DA-6 (3.60 g, 18.0 mmol), followed by the addition of Boc₂O (23.5 g, 108 mmol) dissolved in THF (6.0 g). The mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After the reaction was complete, methanol (10.4 g) was added, and the mixture was stirred at 60 °C for 1 hour. The solvent was then removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g). The mixture was stirred for 30 minutes and then filtered off. The resulting crystals were dried to obtain AD-8 (yield: 5.69 g, 14.2 mmol, 79% yield).

[0125] 1 H-NMR (500MHz) in DMSO-d6: δ (ppm) = 9.27 (s, 2H), 7.41 (d, J = 8.8Hz, 4H), 6.87 (d, J = 9.0Hz, 4H), 1.47 (s, 18H).

[0126] <Example 7: Synthesis of AD-9> Nitrogen replacement was performed by adding THF (20.4 g) to DA-5 (3.60 g, 18.0 mmol), followed by the addition of Boc2O (8.24 g, 37.8 mmol) dissolved in THF (6.0 g). 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 then removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g). The mixture was stirred for 30 minutes, and the crystals were filtered off. The resulting crystals were dried to obtain AD-9 (yield: 5.54 g, 13.9 mmol, 77% yield).

[0127] 1 H-NMR (500MHz) in DMSO-d6: 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).

[0128] <Example 8: Synthesis of AD-10> Relative to tert-butyl 4-hydroxybenzoate (10.0 g, 51.5 mmol), 10% NaOH aq. (200 g) was added as a solvent, and the mixture was heated to 80 °C. Then, 2-chloroethanol (41.5 g, 515 mmol) was added, and the mixture was stirred for 2.5 hours. Then, ethyl acetate (200 g) was added, and the organic layer was extracted and washed separately with pure water and brine (200 g). After extracting the organic layer and filtering out unwanted substances, oil and crystals remained during concentration. Therefore, acetonitrile (70 g) was added, and unwanted substances were filtered out. The filtrate was then concentrated to obtain the target AD-10-1 (yield: 9.20 g, 38.5 mmol, 73% yield).

[0129] 1 H-NMR (500MHz) in DMSO-d6: 7.83 (d, 2H), 7.01 (d, 2H), 4.91 (s, 1H), 4.05 (t, 2H), 3.73 (m, 2H), 1.52 (s, 9H).

[0130] Relative to the previously obtained AD-10-1, THF (70 g) and 4-dimethylaminopyridine (DMAP, 0.351 g, 2.87 mmol) and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC·HCl, 13.2 g, 69 mmol) were added, and the mixture was stirred at room temperature for 10 minutes. Then, adipic acid (2.10 g, 14.4 mmol) was added, and the mixture was stirred at room temperature (25 °C) for one night. After the reaction was complete, the mixture was extracted with ethyl acetate (210 g) and pure water (140 g). The organic layer was concentrated and crystallized with heptane (140 g). After filtering out the white solid and washing the filter cake with heptane, the mixture was dried to obtain AD-10 (yield: 5.50 g, 9.46 mmol, 66% yield).

[0131] 1 H-NMR (500MHz) in DMSO-d6: 7.80 (d, 4H), 6.98 (d, 4H), 4.31 (m, 4H), 4.21 (m, 4H), 2.29 (t, 4H), 1.48 (m, 22H).

[0132] <Example 9: Synthesis of AD-11> Formic acid (30 g) was added relative to AD-10 (2.00 g, 3.41 mmol), and the mixture was stirred at 40 °C for 1 hour. After the reaction was complete, water (60 g) was added, causing crystals to precipitate. The solid obtained through filtration was dried to obtain crude crystals. DMSO (6 g) was added to the crude crystals, and the mixture was heated and stirred at 80 °C. After cooling to room temperature, isopropanol (80 g) was added, causing crystals to precipitate. The crystals obtained through filtration were dried to obtain AD-11 (yield: 0.590 g, 1.24 mmol, 36% yield).

[0133] 1 H-NMR (500MHz) in DMSO-d6: 12.6 (s, 2H), 7.88 (d, 4H), 7.03 (d, 4H), 4.36 (m, 4H), 4.26 (m, 4H), 2.33 (t, 4H), 1.53 (m, 4H).

[0134] [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.

[0135] <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 is 9284, and the Mw is 26834.

[0136] <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 adding 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.

[0137] <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 introducing 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, thereby 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.

[0138] <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.

[0139] The types and amounts of the tetracarboxylic acid and diamine components used in the above synthetic examples 1 to 5 are shown in Table 1. It should be noted that in Table 1, the values ​​of the tetracarboxylic acid and diamine components represent the proportion (mole parts) of each compound relative to 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 the mixture was stirred at room temperature for 24 hours to obtain a polyamic acid solution (A-6) with a non-amino-terminated structure.

[0140] [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.

[0141] <Examples 2-11 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-11) of Examples 2 to 11 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 Additives, and Other Additives represent the proportions (parts by mass) of each polymer solid component and additive relative to the total 100 parts by mass of the polymer components.

[0142] [Making of LCD Cells] <Fabrication of ECB-type LCD Cells> A liquid crystal cell with an ECB mode liquid crystal display element was manufactured.

[0143] 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.

[0144] 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.

[0145] <Fabrication of FFS-driven LCD cell> A liquid crystal cell with an FFS mode liquid crystal display element was manufactured.

[0146] 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 thickness of the second SiN film is 300nm, which serves 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 electrode-bearing substrate has a structure where the first common electrode and the third pixel electrode are insulated from each other by the second SiN film.

[0147] The third-layer pixel electrode has a comb-like shape formed by multiple electrode lines arranged in parallel at 6μm intervals, with the central portion bent at an inner angle of 160°. Each pixel is formed by multiple electrode lines, and there are a first region and a second region bounded by the line connecting the bent portions.

[0148] 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 substrate (hereinafter referred to as the electrode substrate) and a glass substrate with columnar spacers having a height of 4 μm on the back side having an ITO film formed thereon (hereinafter referred to as the opposing substrate). 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). Afterwards, it was ultrasonically cleaned in pure water for 1 minute, water droplets were removed by airflow, and it was dried at 80°C for 10 minutes to obtain a substrate with a liquid crystal alignment film. It should be noted that the liquid crystal alignment film formed on the electrode substrate is aligned 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. The liquid crystal alignment film formed on the opposing substrate is aligned 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) is printed onto the substrates using a dispensing machine. Another substrate is then bonded together with its respective liquid crystal alignment film aligned at 0° and facing each other. The bonded substrates are then pressed together, and the sealant is cured by heating in a 150°C hot air circulating oven for 60 minutes to produce an empty cell. Negative liquid crystal NA-1559 (DIC) is injected into the empty cell using a depressurized injection method, and the injection port is sealed, thus obtaining an FFS-driven liquid crystal cell. The resulting liquid crystal cell is then heated at 120°C for 1 hour and placed at 23°C overnight for evaluation.

[0149] [Characteristics Evaluation of LCD Cells] The characteristics of the ECB-type liquid crystal cell and the FFS-driven liquid crystal cell manufactured above are evaluated as follows.

[0150] <Evaluation of Orientation Stability Based on Long-Term Communication> This evaluation assesses the image retention (also known as AC image retention) caused by the deterioration of the alignment performance of the liquid crystal alignment film during long-term AC driving.

[0151] Using the FFS-driven liquid crystal cell fabricated above, a high-brightness backlight with a surface temperature of 50℃ (light source: LED, brightness: 30000 cd / m²) was used. 2An AC voltage of ±6.5V at a frequency of 30Hz was applied to the liquid crystal cell for 120 hours. Afterwards, the pixel electrodes and common electrode of the liquid crystal cell were short-circuited, and the cell was left at room temperature (23°C) for one day. Following this, the liquid crystal cell was placed between two polarizing plates orthogonally arranged along their polarization axes. The backlight was previously turned on without any voltage applied. The arrangement angle of the liquid crystal cell was adjusted to minimize the transmitted light intensity in the first region of the first pixel. Then, the rotation angle required to minimize the transmitted light intensity in the second region of the first pixel was calculated as angle Δ. The same angle Δ was calculated by comparing the first and second regions in the second pixel. Finally, the average of the angles Δ for the first and second pixels was calculated as the rotation angle Δ of the liquid crystal cell. It can be said that the smaller the value of this rotation angle Δ, the better the stability of the liquid crystal alignment.

[0152] <Determination of Pretilt Angle> The pretilt angle within the ECB-type liquid crystal cell was determined using the AxoScan from Axometrics and the Mueller matrix method. A lower pretilt angle indicates better viewing angle characteristics.

[0153] The evaluation results of the orientation stability and pretilt angle of each liquid crystal alignment agent used in Examples 1 to 6 and Comparative Examples 1 to 4 are shown in Table 3.

[0154] 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 adding specific additives as additives has better alignment stability and viewing angle characteristics compared with the liquid crystal alignment film obtained by not adding specific additives or other additives. (Comparison of Examples 1-5 and Examples 8-11 with Comparative Example 1, and Comparison of Examples 6 and Examples 7 with Comparative Example 4).

[0155] On the other hand, when other additives are added, compared with liquid crystal alignment films obtained from liquid crystal alignment agents that have not added any specific additives or other additives, there are cases where either alignment stability or viewing angle characteristics are improved, but not all of them are good. (Comparison of Comparative Examples 2-3 with Comparative Example 1).

[0156] 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.

[0157] It should be noted that the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-052112, filed on March 27, 2024, are incorporated herein as a disclosure of the specification of this invention.

Claims

1. A liquid crystal alignment agent comprising components A and B as described below, Component A: Polymer A with the ability to orient liquid crystals; Component B: Compound B as shown in formula (1) below; In equation (1), Ar1 and Ar 1’ Each of these elements 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 with monovalent groups, wherein... The monovalent groups do 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, methyl, trifluoromethyl or hydroxyl, and in the presence of multiple Y1s, the multiple Y1s are optionally the same 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) below. 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) 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-C(R) q1 In )2-*2, *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; * indicates that it is related to Ar1 or Ar 1’ Bonded bonds.

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 (q2-2), (q3-1) to (q3-3), and (q4-1) to (q4-2). 。 3. The liquid crystal alignment agent according to claim 1, wherein, The polymer A is at least one polymer selected from the group consisting of a polyimide precursor and a polyimide that is an imide derivative of the polyimide precursor.

4. The liquid crystal alignment agent according to claim 3, wherein, The polyimide precursor is obtained using a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof as shown in formula (2) below. In equation (2), Z represents a structure selected from the following equations (x-1) to (x-13). In the above formula, R 1 ~R 4 Each can 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, or a phenyl group; R 5 and R 6 Each A1 and A2 independently represent a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A1 and A2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group; the two A2 groups may be the same or different; *1 is a bond bonded to the anhydride group of one party, and *2 is a bond bonded to the anhydride group of the other party.

5. The liquid crystal alignment agent according to claim 4, wherein, The expression (x-1) is selected from the group consisting of the following expressions (x1-1) to (x1-6). In the above formula, *1 is a bond bonded to the anhydride group of one side, and *2 is a bond bonded to the anhydride group of the other side.

6. The liquid crystal alignment agent according to claim 3, wherein, The polyimide precursor is obtained using a diamine component containing at least one diamine selected from the diamines shown in formula (3) and formula (3A) below. In formula (3), Y3 represents the divalent organic group shown in formula (O) below, and in formula (3A), Y 3a The following formula (a) represents a divalent organic group; each of the multiple Rs independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; In formula (O), Ar represents a divalent benzene ring, a biphenyl structure, a naphthalene ring, or an aromatic heterocycle; in the presence of multiple Ars, the two Ars may be identical or different, and any hydrogen atom of the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle may be substituted with a monovalent substituent; p is an integer of 0 or 1; Q3 represents -(CH2). n - or as stated - (CH2) n A group consisting of at least a portion of -CH2- being replaced by any one of -O-, -C(=O)-, or -O-C(=O)-; * indicates a bond, wherein the -(CH2-) group is... n In this context, n is an integer from 2 to 18; In formula (a), the hydrogen atom on the benzene ring is optionally substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms; P is an aromatic ring selected from any of the benzene ring or biphenyl structures, and the hydrogen atom on the benzene ring or biphenyl structure is optionally substituted with a methyl or fluorine atom; n is an integer from 0 to 5; when n is an integer greater than 2, n Ps independently have the above definition; * denotes a bond.

7. The liquid crystal alignment agent according to claim 6, wherein, The divalent organic group represented by formula (O) is any group from formulas (o-1) to (o-12) below. In the formula, X1 and X2 independently represent single bonds or -O-. In equation (o-7), each X7 independently represents a single bond or -O-; wherein, when n is 1, at least one of the two X7s represents -O-; in equation (o-12), each of the two m independently has the above definition.

8. The liquid crystal alignment agent according to claim 3, wherein, The polyimide precursor is obtained using a diamine component containing a structure of a diamine having at least one nitrogen-containing atom selected from the group consisting of a heterocycle containing a nitrogen atom, a secondary amino group, and a tertiary amino group, wherein the nitrogen-containing heterocycle does not include the imide ring present in the polyimide.

9. 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.

10. The liquid crystal alignment agent according to claim 1, wherein, The liquid crystal alignment agent further comprises at least one additive selected from the group consisting of a binding agent, a crosslinking compound, and a dielectric or conductive material used to adjust the dielectric constant or resistance of the liquid crystal alignment film.

11. A method for manufacturing a liquid crystal alignment film, wherein, The liquid crystal alignment agent as described in any one of claims 1 to 10 is coated onto a substrate, and then fired to align the resulting film.

12. A liquid crystal alignment film formed from a liquid crystal alignment agent as described in any one of claims 1 to 10.

13. A liquid crystal display element comprising the liquid crystal alignment film as described in claim 12.

14. The liquid crystal display element according to claim 12, wherein, The liquid crystal display element is driven by either IPS or FFS.

15. A compound represented by any one of the following formulas: (q1-1) to (q1-5), (q2-1) to (q2-2), (q3-1) to (q3-3), and (q4-1) to (q4-2). 。

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