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

Abstract

Provided are: a liquid crystal-aligning agent from which it is possible to obtain a liquid crystal alignment film which has excellent printability and in which the amount of accumulated electric charge is less; a liquid crystal alignment film obtained from the liquid crystal-aligning agent; and a liquid crystal display element using the liquid crystal alignment film.　This liquid crystal-aligning agent contains a (A) component and a (B) component. (A) component: A polymer (A) having the ability to align liquid crystals. (B) component: A compound (B) represented by formula (1). In formula (1), Ar1 and Ar1' each independently represent a benzene ring, a biphenyl structure, or a naphthalene ring. At least one hydrogen atom on the benzene ring, the biphenyl structure, or the naphthalene ring is optionally substituted with a monovalent group (excluding (q1)-(q4), and a hydroxy group, a methylol group, or an alkoxy group). X represents a divalent organic group represented by formula (2). (2): *-X1-(Y1-L)n-*

Description

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

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

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

[0003] WO2022 / 220199 publication

[0004] A liquid crystal display element generally includes 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 alignment of liquid crystal molecules in the liquid crystal layer, and thin film transistors (TFTs) that switch electrical signals supplied to the pixel electrodes. In recent years, large-screen, high-definition liquid crystal display elements have become mainstream, and display element standards with increased pixel counts, such as 4K and 8K, have been created. Liquid crystal alignment films are required to have the ability to ensure a uniform film thickness even over surface irregularities on substrates equipped with TFTs, and liquid crystal alignment agents with better printability than conventional liquid crystal alignment agents are needed.

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

[0006] In view of the above, an object of the present invention is to provide a liquid crystal alignment agent that can produce a liquid crystal alignment film that has excellent printability and a small amount of accumulated charge, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element using the liquid crystal alignment film.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by using a specific compound, and have thus completed the present invention.

[0008] The present invention relates to a liquid crystal aligning agent characterized by containing the following components (A) and (B): a liquid crystal alignment film obtained from the liquid crystal aligning agent; a liquid crystal display device having the liquid crystal alignment film; and a novel compound used in the liquid crystal aligning agent. Component (A): a polymer (A) capable of aligning liquid crystals; Component (B): a compound (B) represented by the following formula (1): (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4), a hydroxy group, a methylol group, or an alkoxy group). X is a divalent organic group represented by the following formula (2): *-X １ -(Y １ -L) ｎ -* (2) (In formula (2), X １ , L is a single bond, —O—, or “—NR Ａ -" (However, R Ａrepresents a hydrogen atom or a monovalent organic group. When a plurality of L's are present, the plurality of L's may be the same or different. However, X １ is a single bond, and n is an integer of 1 to 6, １ The total number of carbon atoms and heteroatoms in n Ls is 2 or more, and n is an integer of 0 to 6. １ represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups. １ If there are multiple Y １ may be the same as or different from each other.) Q and Q' satisfy either of the following conditions (1) and (2). (1) Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4). When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ５ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group having 1 to 30 carbon atoms. The monovalent organic group is bonded to the carbon atom of the carbonyl group via an oxygen atom, a nitrogen atom, or a carbon atom, and satisfies either of the following conditions (a) or (b): (a) it has a leaving group that is released by heating; (b) R １ has at least one carboxy group. ２ represents a hydrogen atom or a monovalent organic group. ３ represents a leaving group that is eliminated by heating. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a carboxy group. (2) Q and Q' each independently represent a hydroxy group, a methylol group, or an alkoxy group.

[0009] In this specification, * represents a bond in all cases. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Preferred examples of carbamate protecting groups include tert-butoxycarbonyl groups and 9-fluorenylmethoxycarbonyl groups.

[0010] According to the present invention, a liquid crystal aligning agent capable of producing a liquid crystal alignment film with excellent printability and a small amount of accumulated charge, the liquid crystal alignment film, and a liquid crystal display element having the liquid crystal alignment film are obtained. The mechanism by which the above-mentioned effects of the present invention are obtained is not entirely clear, but the following is thought to be one of the reasons. First, the molecular weight of compound (B) is relatively small, which allows smooth molecular movement within the film during the drying process, making it easy to obtain a smooth coating film. Furthermore, the presence of compound (B), which is a compound with a relatively small molecular weight, in the vicinity of polymer (A) or the introduction of compound (B) into the structure of polymer (A) results in a dense coating film, which increases the electrical resistance of the entire film, which is thought to be the reason for the above-mentioned effects.

[0011] <Component (A)> The liquid crystal aligning agent of the present invention, like known ones, contains a polymer (A) that is a polymer capable of aligning liquid crystals. However, such a polymer is not particularly limited as long as it has the ability to align liquid crystals. The liquid crystal aligning agent of the present invention may contain one or more such polymers. Examples of the polymer (A) include polyimide precursors, polyimides that are imidized products of polyimide precursors, acrylic polymers, methacrylic polymers (hereinafter, acrylic polymers and methacrylic polymers are also collectively referred to as "(meth)acrylic polymers"), acrylamide polymers, methacrylamide polymers (hereinafter, acrylamide polymers and methacrylamide polymers are also collectively referred to as "(meth)acrylamide polymers"), polystyrene, polysiloxane, polyamide, polyester, polyurethane, polycarbonate, polyurea, polyphenol (novolac resin), maleimide polymers, and polymers into which a compound having an isocyanuric acid skeleton or a triazine skeleton has been introduced.

[0012] Examples of raw materials for producing these polymers include the following: When the polymer is a polyimide precursor such as polyamic acid or polyamic acid ester, or a polyimide, at least one tetracarboxylic acid dianhydride selected from tetracarboxylic acids or derivatives thereof, and a diamine; When the polymer is a (meth)acrylic polymer, (meth)acrylic acid or a derivative thereof, or a (meth)acrylic acid ester or a derivative thereof; When the polymer is a (meth)acrylamide polymer, (meth)acrylamide or a derivative thereof;

[0013] When the polymer is polystyrene, styrene or a derivative thereof; When the polymer is polysiloxane, a silane compound having a methoxy group or an ethoxy group; When the polymer is polyamide, at least one dicarboxylic acid component selected from dicarboxylic acids and their derivatives and a diamine component; When the polymer is polyester, at least one dicarboxylic acid component selected from dicarboxylic acids and their derivatives and a diol component; When the polymer is polyurethane, a compound having an isocyanate group and a compound having a hydroxyl group; When the polymer is polycarbonate, a bisphenol derivative and phosgene or a phosgene equivalent (e.g., trichlorophosgene) or diphenyl carbonate;

[0014] If the polymer is polyurea, it is a bisisocyanate derivative and a diamine component; if the polymer is polyphenol (novolac resin), it is a phenol compound component and an aldehyde compound component; if the polymer is a maleimide polymer, it is a maleimide derivative alone or copolymerized with styrene; if the polymer is a polymer into which a compound having an isocyanuric acid skeleton or a triazine skeleton has been introduced, it is a compound having an isocyanuric acid skeleton or a triazine skeleton.

[0015] <Polyimide-Based Polymer> As the polymer (A) contained in the liquid crystal aligning agent of the present invention, from the viewpoints of practicality as a liquid crystal aligning agent, mechanical strength of the coating film, and liquid crystal alignment property, at least one polymer selected from the group consisting of polyimide precursors and polyimides, which are imidized products of polyimide precursors (hereinafter also referred to as polyimide-based polymers), is preferred. The polyimide-based polymer can be produced by a known method. For example, a polyamic acid, which is a polyimide precursor, can be obtained by polymerizing (condensing) a tetracarboxylic acid component consisting of a tetracarboxylic acid dianhydride or a derivative thereof with a diamine component, and a polyimide can be obtained by imidizing this polyimide precursor. Examples of derivatives of tetracarboxylic acid dianhydrides include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.

[0016] <Tetracarboxylic Acid Component> Examples of polyamic acids that serve as polyimide precursors include those obtained from a tetracarboxylic acid component containing an aromatic, acyclic aliphatic, or alicyclic tetracarboxylic acid dianhydride or a derivative thereof. The above tetracarboxylic acid dianhydrides or derivatives thereof may be used singly or in combination of two or more. Here, the aromatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The acyclic aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it is not necessary for the polyamic acid to be composed solely of a chain hydrocarbon structure; it may also contain an alicyclic structure or an aromatic ring structure as part of the structure.

[0017] Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, they do not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure or an aromatic ring structure.

[0018] Among these, the polyamic acid is preferably one obtained using a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (2) or a derivative thereof. (In formula (2), Z represents a structure selected from the following formulas (x-1) to (x-13).) (In the above formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, phenylene, a sulfonyl group, or an amide group. ２ may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.)

[0019] Preferred specific examples of the tetracarboxylic dianhydride or derivative thereof represented by the above formula (2) include those in which X is selected from the above formulae (x-1) to (x-8) and (x-10) to (x-13).

[0020] The above formula (x-1) is preferably selected from the group consisting of the following formulae (x1-1) to (x1-6). (In the above formula, *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.)

[0021] Preferred specific examples of the above formulae (x-12) and (x-13) include the following formulae (x-14) to (x-29), in which "*" indicates the bonding position.

[0022] The amount of the tetracarboxylic dianhydride represented by the above formula (2) or a derivative thereof used is preferably 60 to 100 mol %, more preferably 80 to 100 mol %, and even more preferably 90 to 100 mol %, relative to 1 mol of the total tetracarboxylic acid components to be reacted with the diamine component.

[0023] <Diamine Component> The diamine component used in the production of the polyimide precursor is not particularly limited, but a diamine component containing at least one diamine selected from diamines represented by the following formula (3) or (3A) (hereinafter, these may also be referred to as diamine (H)). The diamines contained in the diamine component may be used alone or in combination of two or more. (In formula (3), Y ３ represents a divalent organic group represented by the following formula (O), and in formula (3A), Y ３ａ represents a divalent organic group represented by the following formula (a): 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, biphenyl structure, naphthalene ring, or aromatic heterocycle. When a plurality of Ars are present, the two Ars may be the same 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. Q ３ Ha-(CH ２ ) ｎ -(n is an integer of 2 to 18), or the above-(CH ２ ) ｎ -of-CH ２ represents a group in which at least a portion of - has been replaced with either -O-, -C(=O)- or -O-C(=O)-. (In formula (a), a hydrogen atom on the benzene ring may be 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 a benzene ring or a biphenyl structure, and a hydrogen atom on the benzene ring or the biphenyl structure may be substituted with a methyl group or a fluorine atom. n is an integer of 0 to 5. When n is an integer of 2 or greater, n Ps independently have the above definition.)

[0024] Examples of the substituent on the benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle in the above formula (O) include 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, a fluoroalkoxy group having 1 to 10 carbon atoms, a carboxy group, a hydroxy group, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a cyano group, and a nitro group.

[0025] Preferred specific examples of the aromatic heterocycle in the above formula (O) include aromatic heterocycles exemplified as nitrogen atom-containing heterocycles described below, of which a pyridine ring, a pyrimidine ring, a pyrazine ring, a benzimidazole ring, or a quinoline ring is preferred.

[0026] From the viewpoint of enhancing liquid crystal alignment properties, the divalent organic group represented by the formula (O) is preferably a divalent organic group represented by any one of the following formulae (o-1) to (o-12): In addition, the hydrogen atoms on the rings in the following formulae (o-1) to (o-10) and (o-12) may be substituted with the substituents exemplified for the diamine (H) above.

[0027] (In the formula, X １ , X ２ each independently represents a single bond or —O—.

[0028] (In formula (o-7), X ７ Each independently represents a single bond or —O—. However, when n is 1, two X ７At least one of represents —O—. In formula (o-12), two m's each independently have the above definition.

[0029] The divalent organic group represented by formula (a) in formula (3A) is preferably a divalent organic group represented by any of the following formulae (A-1) to (A-5) from the viewpoint of enhancing liquid crystal alignment properties.

[0030] The total proportion of at least one diamine selected from the diamines represented by formula (3) or formula (3A) is preferably 1 to 95 mol %, more preferably 1 to 90 mol %, and even more preferably 5 to 90 mol %, relative to 1 mol of the diamine component.

[0031] In order to increase the voltage holding ratio of the resulting liquid crystal alignment film, the polyimide polymer used in the present invention may have at least one nitrogen atom-containing structure (hereinafter also referred to as a specific nitrogen atom-containing structure) selected from the group consisting of a nitrogen atom-containing heterocycle (excluding imide rings contained in polyimides), a secondary amino group, and a tertiary amino group. The polyimide polymer having the specific nitrogen atom-containing structure can be obtained by using a monomer having a nitrogen atom-containing structure, for example, a diamine having the specific nitrogen atom-containing structure, as at least a part of the raw material.

[0032] Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, an indole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a naphthyridine ring, a quinoxaline ring, a phthalazine ring, a triazine ring, a carbazole ring, an acridine ring, a piperidine ring, a piperazine ring, a pyrrolidine ring, a hexamethyleneimine ring, etc. Among these, a pyridine ring, a pyrimidine ring, a pyrazine ring, a benzimidazole ring, a piperidine ring, a piperazine ring, a quinoline ring, a carbazole ring, or an acridine ring is preferred.

[0033] The secondary amino group and tertiary amino group that the diamine having the specific nitrogen atom-containing structure may have are, for example, represented by the following formula (n).

[0034] In the above formula (n), R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. "*1, *2" represent bonds bonded to the hydrocarbon group.

[0035] Examples of the monovalent hydrocarbon group represented by R in the above formula (n) 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.

[0036] Specific examples of diamines having a specific nitrogen atom-containing structure include, in addition to the above-mentioned diamine (H) having an aromatic heterocycle, 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 represented by the following formulae (Dp-1) to (Dp-7), and compounds represented by the following formulae (z-1) to (z-19). (X ３ , X ４ are each independently a single bond or -(CH ２ ) n-(n is an integer of 1 to 4).

[0037]

[0038]

[0039] From the viewpoint of increasing the voltage holding ratio of the liquid crystal display element, the use ratio of the diamine having the specific nitrogen atom-containing structure is preferably 1 mol % or more, more preferably 2 mol % or more, based on the total amount of diamines used in the synthesis, and the use ratio is preferably 90 mol % or less, more preferably 80 mol % or less.

[0040] The polyimide polymer used in the present invention may contain diamines other than the diamines described above (hereinafter also referred to as "other diamines"). Examples of other diamines are given below, but the present invention is not limited to these. Diamines having a group "-N(D)- (D represents a carbamate protecting group)" in the molecule and having 6 to 30 carbon atoms excluding D; 4,4'-diaminoazobenzene and diamines of the following formula (d Ｔ -1) to (d Ｔ-3), diamines having a photoalignment group such as diamines represented by the following formulae (3i-1) to (3i-5); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 1,4-bis(4-aminobenzyl)benzene, diamines represented by the following formulae (3i-1) to (3i-5), 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 Diamines having a carboxy group, such as diamine compounds represented by the following formulae (3b-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'-diaminobenzanilide, 4,4'-diaminoazobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H -indene-6-amine; diamines having a urea bond such as diamines represented by the following formulas (h-1) to (h-3); diamines having an amide bond such as diamines represented by the following formulas (h-4) to (h-6); diamines having a photopolymerizable group at the terminal such as 2-(2,4-diaminophenoxy)ethyl methacrylate and 2,4-diamino-N,N-diallylaniline; cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid Diamines having a steroid skeleton, such as cholestenyl benzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines represented by the following formulae (V-1) to (V-6); diamines having a siloxane bond, such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; diamines such as diamines having an oxazoline structure, such as those represented by the following formulae (Ox-1) to (Ox-2); diamines in which two amino groups are bonded to a group represented by any of formulae (Y-1) to (Y-167) described in WO 2018 / 117239, and the like.

[0041] (In formulas (3i-1) to (3i-3), two n's may be the same or different.)

[0042] (In formula (3b-1), A １ is a single bond, -CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３ )-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CON(CH ３ ) - or -N(CH ３ )CO—, m1 and m2 each independently represent an integer of 0 to 4, and m1+m2 represents an integer of 1 to 4. In formula (3b-2), m3 and m4 each independently represent an integer of 1 to 5. In formula (3b-3), A ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5. ３ and A ４ are each independently a single bond, —CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３ )-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CON(CH ３ ) - or -N(CH ３ ) CO—, and m6 represents an integer of 1 to 4.

[0043]

[0044] (In the above formulas (V-1) to (V-6), X ｖ１ ~X ｖ４ , X ｐ１ ~X ｐ２ are each independently -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ３ )-, -NH-, -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—; X ｖ５ is -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—. ａ represents a single bond, —O—, —NH—, —O—(CH ２ ) ｍ -O-, -C(CH ３ ) ２ -, -CO-, -(CH ２ ) ｍ -, -SO ２ -, -O-C(CH ３ ) ２ -, -CO-(CH ２ ) ｍ -, -NH-(CH ２ ) ｍ -, -SO ２ - (CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -NHCO-, -COO-(CH ２ ) ｍ -OCO-, -CONH-, -NH-(CH ２ ) ｍ -NH- or -SO ２ - (CH ２ ) ｍ -SO ２ - (where m represents an integer of 1 to 6), R ｖ１ ~R ｖ４ , R １ａ ~R １ｂeach independently represents 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), two k's may be the same or different.

[0045]

[0046] Examples of diamines having the above group "-N(D)- (D represents a carbamate protecting group)" in the molecule and having 6 to 30 carbon atoms excluding D include compounds represented by the following formulas (5-1) to (5-15) and (5-18) to (5-20). ((5-2) is preferably (5-16) to (5-17).)

[0047] (Boc represents a tert-butoxycarbonyl group.)

[0048] <Component (B)> The liquid crystal aligning agent of the present invention contains a compound (B) represented by the following formula (1). ((In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4), a hydroxy group, a methylol group, or an alkoxy group). X is a divalent organic group represented by the following formula (2): *-X １ -(Y １ -L) ｎ -* (2) (In formula (2), X １ , L is a single bond, —O—, or “—NR Ａ -" (However, R Ａ represents a hydrogen atom or a monovalent organic group. When a plurality of L's are present, the plurality of L's may be the same or different. However, X １ is a single bond, and n is an integer of 1 to 6, １ The total number of carbon atoms and heteroatoms in n Ls is 2 or more, and n is an integer of 0 to 6. １represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups. １ If there are multiple Y １ may be the same as or different from each other.) Q and Q' satisfy either of the following conditions (1) and (2). (1) Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4). When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ５ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group having 1 to 30 carbon atoms. The monovalent organic group is bonded to the carbon atom of the carbonyl group via an oxygen atom, a nitrogen atom, or a carbon atom, and satisfies either of the following conditions (a) or (b): (a) it has a leaving group that is released by heating; (b) R １ has at least one carboxy group. ２ represents a hydrogen atom or a monovalent organic group. ３ represents a leaving group that is eliminated by heating. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a carboxy group.) (2) Q and Q' each independently represent a hydroxy group, a methylol group, or an alkoxy group.

[0049] R in the above formula (q1) １ The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ３ --CO-NR ３ -, -Si(R ３ ) ２ - (However, R ３ is a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, —SO ２ - or the like substituted monovalent group (R１ｂ ), the monovalent hydrocarbon group, or the monovalent group (R １ｂ and a monovalent group in which at least one hydrogen atom bonded to a carbon atom of R is replaced with a substituent (x), and a monovalent group having a heterocycle. １ is bonded to the carbon atom of the carbonyl group via an oxygen atom, a nitrogen atom, or a carbon atom, and satisfies any one of the above conditions (a) and (b). ４ The monovalent organic group in the formula (I) is a monovalent hydrocarbon group having 1 to 30 carbon atoms, and the methylene group of the hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ３ --CO-NR ３ -, -Si(R ３ ) ２ - (However, R ３ is a hydrogen atom or a monovalent organic group having 1 to 6 carbon atoms, —SO ２ - or the like substituted monovalent group (R ４ｂ ), the monovalent hydrocarbon group, or the monovalent group (R ４ｂ and monovalent groups having a heterocycle, in which at least one hydrogen atom bonded to a carbon atom of the formula (I) is replaced with a substituent (x). Examples of the substituent (x) include a halogen atom, a hydroxy group, a nitro group, an amino group, a mercapto group, a nitroso group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, and a sulfo group.

[0050] In formula (q1) and formula (q2), the heating temperature at which the leaving group is eliminated is preferably 70 to 230°C, more preferably 120 to 200°C. １ may be eliminated together with the adjacent carbonyl group.

[0051] In the above formula (2), Y １ is a divalent hydrocarbon group, and examples of the divalent hydrocarbon group include, but are not limited to, a linear or branched alkylene group, —CH═CH—, a phenylene group, or a cyclohexylene group. １From the viewpoint of suitably achieving the effects of the present invention, Y is preferably a hydrocarbon group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, and even more preferably an alkylene group having 2, 4, or 5 carbon atoms. Some or all of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups, and the halogen atoms substituting the hydrogen atoms in the divalent hydrocarbon group are preferably fluorine atoms. １ If there are multiple Y １ may be the same as or different from each other. When a plurality of L's are present, the plurality of L's may be the same as or different from each other. １ is a single bond, and n is an integer of 1 to 6, １ The total number of carbon atoms and heteroatoms in n Ls is at least 2. n is an integer of 0 to 6, preferably 0 to 1.

[0052] The group "*-X" in the above formula (2) １ -(Y １ -L) ｎ More preferred examples of "-*" include a single bond or the following structures: *-O-*, *-NH-*, *-N(CH ３ )-*, *-O-(CH ２ ) ｑ -O-*, *-O-(CH ２ ) ｎ１ -O-(CH ２ ) ｎ２ -O-*, *-(CH ２ ) ｒ *In the above structure, q, n1, and n2 are each independently an integer of 1 to 6. r is an integer of 2 to 6.

[0053] -C(=O)-R in formula (q1) １ (However, R １ is bonded to the carbon atom of the carbonyl group via an oxygen atom. １Preferred specific examples of —C(═O)—R in formula (q1) include a benzyloxy group, a 9-fluorenylmethyloxy group, an allyloxy group, a tert-butoxy group, a group in which one hydrogen atom has been removed from a hydroxy group of an oxime compound, or an organic group in which one hydrogen atom has been removed from a hydroxy group of a phenol compound. １ (However, R １ is bonded to the carbon atom of the carbonyl group via a nitrogen atom. １ Preferred specific examples of —C(═O)—R in formula (q1) include organic groups in which one hydrogen atom has been removed from the nitrogen atom of a nitrogen-containing compound such as a lactam compound, an amine compound, a pyrazole compound, an imidazole compound, or an imide compound. １ (However, R １ is bonded to the carbon atom of the carbonyl group via a carbon atom. １ A preferred example of the alkyl group is an organic group in which one hydrogen atom is removed from a carbon atom of an active methylene compound, or -(CH ２ ) ｎ -COOH (n is an integer of 1 to 6).

[0054] Examples of the oxime compounds include acetoxime, formaldoxime, cyclohexaneoxime, methyl ethyl ketoneoxime, cyclohexanoneoxime, and benzophenoneoxime. Examples of the lactam compounds include ε-caprolactam and γ-butyrolactam. Examples of the phenol compounds include phenol, naphthol, cresol, xylenol, and halogen-substituted phenols. Examples of the amine compounds include primary amines and secondary amines. The amine compound may be any of aromatic amines, aliphatic amines, and alicyclic amines, and may be a monoalkylamine (methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, etc.), a dialkylamine (preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, methylethylamine, methylpropylamine, ethylpropylamine) group, a H ２ N (Boc), HN (Boc) ２ Specific examples include: diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compounds include pyrazole, methylpyrazole, and dimethylpyrazole. Examples of the imidazole compounds include imidazole, 1-methylimidazole, 1-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compounds include maleimide, succinimide, phthalimide, and derivatives thereof.

[0055] R in formula (q2) ３Preferred specific examples of R in formula (q3) include carbamate-based organic groups such as benzyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, and Boc groups. ４ Preferred specific examples of Ar include a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. １ and Ar １’ In the above formula, examples of the monovalent group substituting a hydrogen atom on the benzene ring, the biphenyl structure, or the naphthalene ring include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cyano group, and a nitro group.

[0056] The compound (B) is preferably at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q2-1), (q3-1) to (q3-2), (q4-1), and (2Q-1) to (2Q-3):

[0057] The content of the compound (B) represented by the above formula (1) in the liquid crystal aligning agent of the present invention is preferably 0.1 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the polymer (A).

[0058] <Method for producing polyimide precursor and polyimide> The polyamic acid, which is the polyimide precursor used in the present 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 (polycondensation). For details of the synthesis method of the polyimide precursor and polyimide, see, for example, WO2015 / 012368.

[0059] The polyimide precursor or polyimide may be a terminal-modified polymer obtained by using an appropriate terminal-capping agent together with the tetracarboxylic acid component and diamine as described above during production. Examples of the terminal-modifying agent include acid anhydrides such as acetic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and trimellitic anhydride; di-tert-butyl dicarbonate; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, and 4-aminobenzoic acid; and monoisocyanate compounds such as ethyl isocyanate, phenyl isocyanate, and naphthyl isocyanate. The proportion of the terminal modifier used is preferably 40 parts by mol or less, and more preferably 30 parts by mol or less, per 100 parts by mol of the total of the diamine components used.

[0060] <Solution Viscosity and Molecular Weight of Polymer> The polyamic acid, polyamic acid ester, and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1,000 mPa·s when prepared into a solution of 10 to 15 wt % from the viewpoint of workability, but are not particularly limited thereto. The solution viscosity (mPa·s) of the polymer is a value measured at 25°C using an E-type rotational viscometer for a polymer solution of 10 to 15 wt % concentration prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0061] The weight average molecular weight (Mw) of the polyamic acid, polyamic acid ester, and polyimide, measured by gel permeation chromatography (GPC) in terms of polyethylene glycol oxide, is preferably 1,000 to 500,000, and more preferably 2,000 to 500,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number average molecular weight (Mn) in terms of polyethylene glycol oxide measured by GPC, is preferably 15 or less, and more preferably 10 or less. Having the molecular weight within this range ensures good liquid crystal alignment properties in liquid crystal display elements.

[0062] <Liquid Crystal Aligning Agent> The liquid crystal aligning agent of the present invention contains the polymer (A) capable of aligning liquid crystals and the compound (B) of the above formula (1). The liquid crystal aligning agent of the present invention preferably has a form in which the compound (B) of the above formula (1) is added to a solution in which the polymer (A) capable of aligning liquid crystals is dissolved in a solvent. The content (concentration) of the polymer (A) contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed, but is preferably 1% by mass or more from the viewpoint of forming a uniform and defect-free coating film, and is preferably 10% by mass or less from the viewpoint of storage stability of the solution.

[0063] The solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and methyl ethyl ketone. Examples of suitable good solvents include propanamide, 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, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

[0064] In addition, the solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also called a poor solvent) that improves the coatability when applying the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the solvent to be used in combination are listed below, but are not limited thereto.

[0065] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propyl 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), and the like.

[0066] Among these, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred. The content of the poor solvent is preferably 1 to 80 mass % of the total solvent contained in the liquid crystal aligning agent, more preferably 10 to 80 mass %, and particularly preferably 20 to 70 mass %. The type and content of the poor solvent are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0067] Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, and N-ethyl-2-pyrrolidone and propylene glycol diacetate, N,N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and dipropylene glycol dimethyl ether, N,N-dimethyl lactamide and ethylene glycol monobutyl ether, N,N-dimethyl lactamide and propylene glycol diacetate, N-ethyl-2-pyrrolidone N-methyl-2-pyrrolidone and diethylene glycol diethyl ether, N,N-dimethyl lactamide and 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 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, 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 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, and N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide, and diisobutyl ketone.

[0068] The liquid crystal aligning agent of the present invention may further contain, in addition to the polymer (A) and the compound (B), a component other than the solvent (hereinafter also referred to as an additive component). Examples of such additive components include an adhesion aid for improving the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealant, a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as a crosslinking compound), and a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film. The liquid crystal aligning agent of the present invention may contain one type of such additive component, or may contain two or more types.

[0069] Examples of the crosslinkable compound, from the viewpoint of exhibiting good resistance to AC afterimages and significantly improving film strength, include a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, and a cyclocarbonate group; a hydroxyalkylamide compound; or a compound selected from compounds represented by the following formula (e):

[0070] (In formula (e), A represents an (m+n)-valent organic group having an aromatic ring. m represents an integer of 1 to 6, and n represents an integer of 0 to 4. R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Any hydrogen atom in the aromatic ring may be replaced by 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 same definition as above.)

[0071] Specific examples of the compound having an oxiranyl group include compounds having two or more oxiranyl groups, such as the compound described in paragraph

[0037] of JP-A-10-338880 and compounds having a triazine ring skeleton described in WO 2017 / 170483. Among these, compounds containing a nitrogen atom, such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds represented by the following formulas (r-1) to (r-3), may also be used.

[0072]

[0073] Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO 2011 / 132751.

[0074] Specific examples of the compound having a protected isocyanate group include the compound having two or more protected isocyanate groups described in paragraphs

[0046] to

[0047] of JP 2014-224978 A, and the compound having three or more protected isocyanate groups described in paragraphs

[0119] to

[0120] of WO 2015 / 141598 A, and may also be compounds represented by the following formulas (bi-1) to (bi-3).

[0075]

[0076] Specific examples of compounds having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in JP 2016-200798 A.

[0077] Specific examples of compounds having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph

[0115] of JP-A No. 2007-286597.

[0078] Specific examples of compounds having a group containing a Meldrum's acid structure include compounds having two or more Meldrum's acid structures described in WO 2012 / 091088.

[0079] Specific examples of the compound having a cyclocarbonate group include the compounds described in WO 2011 / 155577.

[0080] Specific examples of the hydroxyalkylamide compound other than the compound represented by formula (1) above include the compounds described in WO 2015 / 072554 and paragraph

[0058] of JP 2016-118753 A, the compounds described in JP 2016-200798 A, and the compounds described in WO 2019 / 142927 A, and may also be compounds represented by the following formulae (hd-1) to (hd-8), and compounds represented by the following formulae (hd1-1) to (hd1-4).

[0081]

[0082]

[0083] Examples of the (m+n)-valent organic group having an aromatic ring for A in formula (e) include an (m+n)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, an (m+n)-valent organic group to which an aromatic hydrocarbon group having 6 to 30 carbon atoms is bonded directly or via a linking group, and an (m+n)-valent group having an aromatic heterocycle. Examples of the aromatic hydrocarbon include benzene and naphthalene. Examples of the aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridine ring. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, and a divalent or trivalent cyclohexane ring. Any hydrogen atom in the alkylene group may be substituted with an organic group such as an alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a trifluoromethyl group. Specific examples include the compounds described in WO 2010 / 074269 and compounds represented by the following formulas (e-1) to (e-10).

[0084]

[0085] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53

[0105] to 55

[0116] of WO 2015 / 060357. Two or more types of crosslinkable compounds may be combined.

[0086] The content of the crosslinkable compound in the liquid crystal aligning 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 aligning agent, and more preferably 1 to 15 parts by mass from the viewpoint of proceeding with the crosslinking reaction and exhibiting good resistance to AC afterimages.

[0087] Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, and N-trimethoxysilylpropyltriethoxysilane. triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,Examples of silane coupling agents include 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. When a silane coupling agent is used, from the viewpoint of exhibiting good resistance to AC afterimages, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent.

[0088] <Liquid crystal alignment film / liquid crystal display element> The liquid crystal alignment film of the present invention is obtained from the liquid crystal aligning agent described above. The liquid crystal alignment film of the present invention can be used as a liquid crystal alignment film for horizontal alignment type or vertical alignment type (VA type) liquid crystal display elements, and is particularly suitable for horizontal alignment type liquid crystal display elements such as IPS type or FFS type. The liquid crystal display element of the present invention is equipped with the liquid crystal alignment film described above. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (4) or steps (1) to (2) and (4).

[0089] <Step (1): Step of Applying Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention is applied to one side of a substrate having a patterned transparent conductive film by an appropriate application method, such as a roll coater method, a spin coat method, a printing method, or an inkjet method. The substrate is not particularly limited as long as it is highly transparent. In addition to glass substrates and silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. In addition, in reflective liquid crystal display elements, an opaque material such as a silicon wafer can be used for only one substrate. In this case, a light-reflecting material such as aluminum can also be used for the electrode. Furthermore, when manufacturing IPS or FFS liquid crystal elements, a substrate having an electrode made of a comb-shaped patterned transparent conductive film or metal film and an opposing substrate having no electrode are used.

[0090] Examples of a method for applying the liquid crystal alignment agent to a substrate and forming a film include screen printing, offset printing, flexographic printing, an inkjet method, and a spray method. Among these, the application and film formation method by the inkjet method is preferably used.

[0091] <Step (2): Step of Baking the Applied Liquid Crystal Alignment Agent> Step (2) is a step of baking the liquid crystal alignment agent applied to the substrate to form a film. After applying the liquid crystal alignment agent to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal alignment agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for removing the solvent from the liquid crystal alignment agent can be, for example, 40 to 180°C. To shorten the process, the temperature can be 40 to 150°C. The baking time is not particularly limited, but can be 1 to 10 minutes or 1 to 5 minutes. When thermally imidizing the amic acid or amic acid ester in the polymer, a baking step can be performed at a temperature range of, for example, 150 to 300°C or 150 to 250°C after the organic solvent removal step. The baking time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. If the thickness of the film-like substance after baking is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, and more preferably 10 to 200 nm.

[0092] <Step (3): Alignment Treatment of the Film Obtained in Step (2)> Step (3) is a step of optionally aligning the film obtained in Step (2). That is, in horizontal alignment type liquid crystal display devices such as IPS mode or FFS mode, the coating film is subjected to an alignment ability imparting treatment. On the other hand, in vertical alignment type liquid crystal display devices such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as is, but the coating film may also be subjected to an alignment ability imparting treatment. Preferred alignment treatment methods for liquid crystal alignment films include rubbing treatment and photo-alignment treatment. Examples of photo-alignment treatment methods include irradiating the surface of the film-like material with radiation polarized in a certain direction, and optionally performing a heat treatment at a temperature preferably between 150 and 250°C to impart liquid crystal alignment (also referred to as liquid crystal alignment ability). The radiation can be ultraviolet light or visible light having a wavelength of 100 to 800 nm. Among these, ultraviolet light having a wavelength of 100 to 400 nm is preferred, and more preferably between 200 and 400 nm.

[0093] The radiation dose is 1 to 10,000 mJ / cm ２ is preferable, and among these, 100 to 5,000 mJ / cm ２ is more preferable. When irradiating with radiation, the substrate having the film-like material may be irradiated while being heated at 50 to 250°C in order to improve the liquid crystal alignment. The liquid crystal alignment film produced in this manner can stably align the liquid crystal molecules in a fixed direction. Furthermore, the liquid crystal alignment film irradiated with polarized radiation by the above method can be contact-treated with water or a solvent, or the liquid crystal alignment film irradiated with radiation can be heat-treated.

[0094] The solvent used in the contact treatment is not particularly limited, as long as it dissolves the decomposition products generated from the film-like material by irradiation with radiation. Specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate. Among these, water, 2-propanol, 1-methoxy-2-propanol, and ethyl lactate are preferred from the viewpoints of versatility and solvent safety. Water, 1-methoxy-2-propanol, and ethyl lactate are more preferred. The solvent may be one type or a combination of two or more types.

[0095] The heat treatment of the coating film irradiated with the radiation is preferably carried out at 50 to 300° C. for 1 to 30 minutes, more preferably at 120 to 250° C. for 1 to 30 minutes.

[0096] <Step (4): Step of preparing a liquid crystal cell> Two substrates on which a liquid crystal alignment film has been formed are prepared as described above, and a liquid crystal is placed between the two substrates arranged opposite each other. Specifically, the following two methods can be mentioned. In the first method, the two substrates are first arranged opposite each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other. Next, the peripheries of the two substrates are bonded together using a sealant, and a liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant to contact the film surface, and then the injection hole is sealed.

[0097] The second method is called the ODF (One Drop Fill) method. A UV-curable sealant, for example, is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. The entire surface of the substrate is then irradiated with UV light to cure the sealant. In either method, it is preferable to further heat the liquid crystal composition used to a temperature at which it assumes an isotropic phase and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling. If the coating film is subjected to a rubbing treatment, the two substrates are positioned opposite each other so that the rubbing directions on each coating film are at a predetermined angle to each other, for example, perpendicular or antiparallel. Examples of sealants that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred.

[0098] 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 the polarizing plate to be attached to the outer surface of the liquid crystal cell include a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0099] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, information displays, etc. In addition, the polymer composition contained in the liquid crystal aligning agent can be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other applications such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.

[0100] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds used and the methods for measuring the properties are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve THF: tetrahydrofuran (Tetracarboxylic acid dianhydrides) CA-1 to CA-4: Compounds represented by the following formulas (CA-1) to (CA-4), respectively (Diamine) DA-1 to DA-6: Compounds represented by the following formulas (DA-1) to (DA-6), respectively (In the above formula, Boc represents a tert-butoxycarbonyl group.) (Additives) AD-1 to AD-7: Compounds represented by the following formulas (AD-1) to (AD-7), respectively. Among the above additives, AD-3 to AD-7 are included in the range of specific additives corresponding to compound (B) of the present application. (In the above formula, Boc represents a tert-butoxycarbonyl group.)

[0101] (Reaction Reagent) Boc ２ O: di-tert-butyl dicarbonate SAH: succinic anhydride Ac ２ O: acetic anhydride

[0102] <Measurement of Viscosity> Measurement was carried out at 25°C using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL and a cone rotor TE-1 (1°34', R24).

[0103] <Measurement of molecular weight> Measurement was carried out using the following room temperature GPC (gel permeation chromatography) apparatus under the following conditions, and Mn and Mw were calculated as polyethylene glycol oxide equivalent values. GPC apparatus: GPC-101 (manufactured by Resonac Corporation), Column: GPC KD-803 and GPC KD-805 (manufactured by Resonac Corporation) connected in series, Column temperature: 50°C, Eluent: N,N-dimethylformamide (containing lithium bromide monohydrate (LiBr.H) as an additive), ２ o-Phosphoric acid (o-Phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L), flow rate: 1.0 mL / min. Standard sample for preparing a calibration curve: EasiVial PEG / PEO polyethylene glycol oxide PL2080-0201 (molecular weight: about 1,500, about 4,000, about 13,000, about 30,000, about 70,000, about 130,000, about 500,000, about 1,000,000, about 1,500,000) (GL Sciences).

[0104] [Synthesis of Additives] AD-5 and AD-6 are novel compounds not yet published in the literature, and the products in the following Additive Synthesis Examples 1 to 5 are １ The product was identified by H-NMR analysis. The analysis conditions were as follows: Apparatus: BRUKER ADVANCE III-500 MHz Measurement solvent: deuterated dimethyl sulfoxide (DMSO-d ６ ) Reference substance: tetramethylsilane (TMS) (δ 0.0 ppm for １ H)

[0105] Additive Synthesis Example 1: Synthesis of AD-3 THF (20.4 g) was added to DA-6 (3.60 g, 18.0 mmol) and purged with nitrogen. Then, Boc ２O (23.5 g, 108 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (10.4 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g), stirred for 30 minutes, and filtered. The obtained crystals were dried to obtain AD-3 (yield: 5.69 g, 14.2 mmol, 79%). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.27 (s, 2H), 7.41 (d, J = 8.8Hz, 4H), 6.87 (d, J = 9.0Hz, 4H), 1.47 (s, 18H).

[0106] Additive Synthesis Example 2: Synthesis of AD-4 THF (20.4 g) was added to DA-5 (3.60 g, 18.0 mmol) and purged with nitrogen. Then, Boc ２ O (8.24 g, 37.8 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (3.63 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator, and the precipitated solid was dispersed in toluene (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-4 (yield: 5.54 g, 13.9 mmol, 77% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.02 (s, 2H), 7.70 (s, 1H), 7.26 (d, J = 8.1Hz, 4H), 6.89 (d, J = 8.9Hz, 4H), 1.46 (s, 18H).

[0107] Additive Synthesis Example 3: Synthesis of AD-5 THF (20.4 g) was added to DA-2 (3.60 g, 14.7 mmol) and purged with nitrogen. Then, Boc ２O (19.3 g, 88.4 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (8.50 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator. The precipitated solid was dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-5 (yield: 5.38 g, 12.1 mmol, 82% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.12 (s, 2H), 7.35 (d, J = 8.5Hz, 4H), 6.87 (d, J = 9.1Hz, 4H), 4.21 (2, 4H), 1.46 (s, 18H).

[0108] Additive Synthesis Example 4: Synthesis of AD-6 To DA-1 (3.00 g, 10.5 mmol), NMP (13.0 g) was added and the mixture was purged with nitrogen. SAH (3.14 g, 31.4 mmol) dissolved in NMP (4.0 g) was then added and the mixture was stirred at room temperature for 1 day to allow the reaction to proceed. After completion of the reaction, the above solution was slowly added dropwise to methanol (300 g) to allow recrystallization, yielding crude crystals. The crude crystals were dispersed in methanol (150 g), stirred for 30 minutes, and the crystals were filtered off. The obtained crystals were dried to obtain AD-6 (yield: 3.47 g, 7.14 mmol, 68% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 12.1 (br, 2H), 9.77 (s, 2H), 7.46 (d, J = 9.1Hz, 4H), 6.85 (d, J=9.1Hz, 4H), 2.51 (m, 8H), 3.93 (t, 4H), 1.75 (m, 4H), 1.54 (m, 2H).

[0109] Additive Synthesis Example 5: Synthesis of AD-7 THF (18.4 g) was added to DA-1 (3.60 g, 12.6 mmol) and purged with nitrogen. Then, Boc ２O (16.5 g, 75.4 mmol) was added and the mixture was stirred at room temperature for 1 day to react. After completion of the reaction, methanol (7.25 g) was added and the mixture was stirred at 60°C for 1 hour, after which the solvent was removed using an evaporator. The precipitated solid was dispersed in methanol (150 g) and stirred for 30 minutes, and the crystals were separated by filtration. The obtained crystals were dried to obtain AD-7 (yield: 3.61 g, 7.43 mmol, 59% yield). １ H-NMR (500MHz) in DMSO-d ６ : δ (ppm) = 9.08 (s, 2H), 7.32 (d, J = 8.4Hz, 4H), 6.82 (d, J = 9.1Hz, 4H), 3.91 (t, 4H), 1.74 (m, 4H), 1.53 (m, 2H), 1.46 (s, 18H).

[0110] [Polymer Synthesis] <Synthesis Example 1> DA-1 (2.29 g, 8.00 mmol) and NMP (16.8 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while supplying nitrogen. Thereafter, CA-1 (1.69 g, 7.54 mmol) and NMP (12.4 g) were added, and the mixture was stirred at 40°C for 18 hours to obtain a solution of polyamic acid (A-1) with a solids concentration of 12% by mass (viscosity: 225 mPa s). The Mn of this polyamic acid was 10,382 and the Mw was 32,874.

[0111] Synthesis Example 2 DA-2 (0.977 g, 4.00 mmol), DA-5 (0.797 g, 4.00 mmol), and NMP (10.1 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (1.50 g, 6.00 mmol) and NMP (8.30 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (0.494 g, 1.68 mmol) and NMP (2.80 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-2) with a solids concentration of 15% by mass (viscosity: 304 mPa s). The Mn of this polyamic acid was 9,284, and the Mw was 26,834.

[0112] Synthesis Example 3: DA-1 (9.74 g, 34.0 mmol), DA-3 (1.37 g, 4.01 mmol), DA-4 (1.11 g, 1.99 mmol), and NMP (106 g) were added to a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-1 (7.89 g, 35.2 mmol) and NMP (41.0 g) were added, and the mixture was stirred at room temperature for 18 hours to obtain a solution of polyamic acid (A-3) with a solids concentration of 12% by mass (viscosity: 210 mPa s). The Mn of this polyamic acid was 10,521, and the Mw was 32,302.

[0113] Synthesis Example 4 DA-5 (10.2 g, 51.0 mmol), DA-2 (8.31 g, 34.0 mmol), and NMP (135 g) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and dissolved by stirring at room temperature while introducing nitrogen. Thereafter, CA-2 (13.8 g, 55.2 mmol) and NMP (47.6 g) were added, and the mixture was stirred at 50 ° C. for 5 hours. Thereafter, after cooling to room temperature, CA-3 (7.45 g, 25.3 mmol) and NMP (41.1 g) were added, and the mixture was stirred at 70 ° C. for 18 hours, to obtain a solution of polyamic acid (A-4) with a solids concentration of 15% by mass (viscosity: 309 mPa s). The Mn of this polyamic acid was 10,357, and the Mw was 26,452. Synthesis Example 5 DA-1 (3.72 g, 13.0 mmol) and NMP (37.3 g) were added to a 50 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was stirred at room temperature while supplying nitrogen to dissolve the mixture. After cooling to room temperature, CA-4 (2.64 g, 12.1 mmol) and NMP (9.30 g) were added, and the mixture was stirred at 50° C. for 18 hours to obtain a solution of polyamic acid (A-5) with a solids concentration of 12 mass%.

[0114] The types and amounts of the tetracarboxylic acid components and diamine components used in Synthesis Examples 1 to 5 are shown in Table 1. In Table 1, the numerical values ​​for the tetracarboxylic acid components and diamine components represent the proportions (parts by mole) of each compound used relative to 100 parts by mole of the total amount of the diamine components used in the synthesis of each polyamic acid.

[0115]

[0116] Synthesis Example 6 To the polyamic acid solution A-3 (20 g), 0.11 g (1.13 mmol) of SAH was added and stirred at room temperature for 24 hours to obtain a solution of polyamic acid (A-6) having a non-amino terminal structure.

[0117] [Preparation of Liquid Crystal Alignment Agent] Example 1 To the solution (1.63 g) of the polyamic acid (A-1) obtained in Synthesis Example 1, the solution (3.90 g) of the polyamic acid (A-2) obtained in Synthesis Example 2, NMP (0.90 g), GBL (6.36 g), BCS (6.00 g), AD-1 (1 mass% GBL solution, 0.78 g), AD-2 (10 mass% NMP solution, 0.39 g), and AD-3 (0.04 g) were added, and the mixture was stirred at room temperature for 2 hours, thereby obtaining a liquid crystal aligning agent (AL-1) of the present invention.

[0118] <Examples 2 to 9 and Comparative Examples 1 to 3> By carrying out the same operation as in Example 1 above, except that the type and amount of polymer solution, solvent, and additive used were changed as shown in Table 2, the liquid crystal aligning agent (AL-2) to (AL-9) of Examples 2 to 9 of the present invention and the liquid crystal aligning agent (AL-C1) to (AL-C3) of Comparative Examples 1 to 3 were obtained.

[0119]

[0120] In Table 2, the numerical values ​​for Polymer 1, Polymer 2, Additive 1, Additive 2, Specific Additive, and Other Additives represent the proportions (parts by mass) of each polymer solid content and additive relative to 100 parts by mass of the total polymer components.

[0121] <Fabrication of FFS-Driven Liquid Crystal Cell> A liquid crystal cell with the configuration of an FFS-mode liquid crystal display element was fabricated. First, a substrate with electrodes was prepared. The substrate was a rectangular glass substrate measuring 30 mm x 50 mm and 0.7 mm thick. A solid-patterned ITO electrode constituting a common electrode was formed on the substrate as a first layer. A SiN (silicon nitride) film deposited by CVD (chemical vapor deposition) was formed on the first common electrode as a second layer. The second SiN film had a thickness of 300 nm, which served as an interlayer insulating film. A comb-shaped pixel electrode formed by patterning an ITO film as a third layer was disposed on the second SiN film. Two pixels, a first pixel and a second pixel, were formed, each measuring 10 mm long and 5 mm wide. This electrode-equipped substrate had a structure in which the first common electrode and the third pixel electrode were insulated by the second SiN film. The pixel electrode of the third layer had a comb-like shape with the central portion bent at an interior angle of 160° and multiple electrode lines, each 3 μm wide, arranged parallel to each other at intervals of 6 μm. One pixel was formed by multiple electrode lines and had a first region and a second region separated by a line connecting the bent portions.

[0122] Next, the liquid crystal alignment agent obtained above was filtered through a filter with a pore size of 1.0 μm, and then spin-coated onto the electrode-attached substrate (hereinafter referred to as the electrode substrate) and a glass substrate (hereinafter referred to as the counter substrate) having a 4 μm-high columnar spacer with an ITO film formed on the backside. After drying for 2 minutes on a hot plate at 80 ° C, it was baked for 20 minutes in a hot air circulating oven at 230 ° C to form a coating film with a thickness of 60 nm. This coating film was subjected to a rubbing alignment treatment (roller diameter: 120 mm, roller rotation speed: 1000 rpm, movement speed: 20 mm / sec, indentation length: 0.4 mm) using a rayon cloth (HY-5318 manufactured by Hyperflex). The substrate was then ultrasonically cleaned in pure water for 1 minute, water droplets were removed by air blowing, and the substrate was dried at 80 ° C for 10 minutes to obtain a substrate with a liquid crystal alignment film. The liquid crystal alignment film formed on the electrode substrate was subjected to an alignment treatment so that the direction dividing the interior angle of the pixel bend was parallel to the liquid crystal alignment direction. The liquid crystal alignment film formed on the counter substrate was also subjected to an alignment treatment so that the alignment direction of the liquid crystal on the electrode substrate was aligned with the alignment direction of the liquid crystal on the counter substrate when the liquid crystal cell was fabricated. The two substrates were combined into a pair, and a sealant (Mitsui Chemicals XN-1500T) was printed on one substrate using a dispenser. Another substrate was then attached to the other substrate, facing each other with the alignment directions of the liquid crystal alignment films aligned at 0°. The bonded substrates were then pressed together and heated for 60 minutes in a hot air circulating oven at 150°C to cure the sealant, producing an empty cell. Negative liquid crystal NA-1559 (DIC Corporation) was injected into this empty cell using a vacuum injection method, and the injection port was sealed to obtain an FFS-driven liquid crystal cell. The resulting liquid crystal cell was then heated at 120°C for 1 hour and left overnight at 23°C before being used for evaluation.

[0123] [Evaluation of Liquid Crystal Cell Characteristics] The characteristics of the FFS drive liquid crystal cell prepared above were evaluated as follows.

[0124] <Evaluation of Charge Accumulation Amount by AC Drive> The FFS-driven liquid crystal cell prepared above was placed between two polarizing plates arranged with their polarization axes perpendicular to each other. With the pixel electrode and the common electrode shorted and at the same potential, an LED backlight was irradiated from below the two polarizing plates. The angle of the liquid crystal cell was adjusted so that the luminance of the LED backlight transmitted through the two polarizing plates was minimized. Next, a 60 Hz AC voltage was applied to the liquid crystal cell, and the VT curve (voltage-transmittance curve) was measured. The AC voltage at which the relative transmittance was 23% was calculated as the driving voltage. For image retention evaluation, the liquid crystal cell was driven for 60 minutes by applying a 60 Hz AC voltage at which the relative transmittance was 100%. Then, an AC voltage at which the relative transmittance was 23% was applied, and the DC voltage was swept to measure the applied voltage at which display flicker was minimized. The absolute value of the applied voltage at which display flicker was minimized was defined as the charge accumulation amount. The smaller the charge accumulation amount, the better. The evaluation of the afterimage according to the above-mentioned method was carried out under a temperature condition in which the temperature of the liquid crystal cell was 45°C.

[0125] [Evaluation of Coatability] The liquid crystal alignment agent obtained above was applied by spin coating to an ITO substrate measuring 100 mm x 100 mm and having a thickness of 1.1 mm. After drying on a hot plate at 80°C for 2 minutes, the substrate was baked in a hot air circulating oven at 230°C for 20 minutes to obtain a substrate with a liquid crystal alignment film having a thickness of 60 nm. When the substrate with the liquid crystal alignment film was observed with the naked eye, if the coating surface was uniform and free of unevenness, it was rated as "good," and if unevenness was visible on the coating surface, it was rated as "poor."

[0126] Table 3 shows the evaluation results of the charge accumulation amount and the coatability using each of the liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2. The numbers in parentheses for the polymer components and additives represent the blending ratio (parts by mass) of each polymer solid content and additive when the total content of the polymer solid content is 100 parts by mass.

[0127]

[0128] As shown in Table 3, the liquid crystal alignment films obtained from the liquid crystal alignment agent containing the specific additive had better charge storage capacity and coatability than the liquid crystal alignment films obtained from the liquid crystal alignment agent containing neither the specific additive nor other additives. Examples 1 to 5, 8, and 9 (charge storage capacity of 309 mV or less) were able to obtain liquid crystal cells exhibiting superior charge storage capacity compared to Comparative Example 1 (charge storage capacity of 310 mV) and Comparative Example 3 (charge storage capacity of 328 mV). Furthermore, Examples 6 (charge storage capacity of 281 mV) and 7 (charge storage capacity of 291 mV) were able to obtain liquid crystal cells exhibiting superior charge storage capacity compared to Comparative Example 2 (charge storage capacity of 304 mV).

[0129] The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention can be suitably used in various liquid crystal display elements, typified by liquid crystal display elements of an IPS drive system or an FFS drive system. These display elements are not limited to liquid crystal displays intended for display purposes, and can also be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other purposes, such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.

[0130] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-052139 filed on March 27, 2024 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent containing the following components (A) and (B): Component (A): a polymer (A) capable of aligning liquid crystals; Component (B): a compound (B) represented by the following formula (1): (In formula (1), Ar １ , and Ar １’ each independently represents a benzene ring, a biphenyl structure, or a naphthalene ring, and one or more hydrogen atoms on the benzene ring, the biphenyl structure, or the naphthalene ring may be substituted with a monovalent group (excluding (q1) to (q4), a hydroxy group, a methylol group, or an alkoxy group). X is a divalent organic group represented by the following formula (2): *-X １ -(Y １ -L) ｎ -* (2) (In formula (2), X １ , L is a single bond, —O—, or “—NR Ａ -" (However, R Ａ represents a hydrogen atom or a monovalent organic group. When a plurality of L's are present, the plurality of L's may be the same or different. However, X １ is a single bond, and n is an integer of 1 to 6, １ The total number of carbon atoms and heteroatoms in n Ls is 2 or more, and n is an integer of 0 to 6. １ represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and some of the hydrogen atoms in the divalent hydrocarbon group may be substituted with halogen atoms, methyl groups, trifluoromethyl groups, or hydroxy groups. １ If there are multiple Y １ may be the same as or different from each other.) Q and Q' satisfy either of the following conditions (1) and (2). (1) Q and Q' each independently represent a hydrogen atom or a monovalent group selected from the group consisting of the following (q1) to (q4). When formula (1) has a plurality of (q1) to (q4), a plurality of R １ ~R ５ may be the same as or different from each other. (In formula (q1), R １ represents a monovalent organic group having 1 to 30 carbon atoms. The monovalent organic group is bonded to the carbon atom of the carbonyl group via an oxygen atom, a nitrogen atom, or a carbon atom, and satisfies either of the following conditions (a) or (b): (a) it has a leaving group that is released by heating; (b) R １ has at least one carboxy group. ２ represents a hydrogen atom or a monovalent organic group. ３ represents a leaving group that is eliminated by heating. ４ represents a hydrogen atom, a hydroxy group, a halogen atom, or a monovalent organic group. ５ represents a carboxy group.) (2) Q and Q' each independently represent a hydroxy group, a methylol group, or an alkoxy group.

2. The liquid crystal aligning agent according to claim 1, wherein the compound (B) is at least one compound selected from the group consisting of the following formulae (q1-1) to (q1-5), (q3-1) to (q3-2), (q4-1), and (2q-1) to (2q-3): (Boc represents a tert-butoxycarbonyl group.) 3. The liquid crystal aligning agent according to claim 1, wherein the polymer (A) is at least one polymer selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors.

4. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride represented by the following formula (2) or a derivative thereof: (In formula (2), Z represents a structure selected from the following formulas (x-1) to (x-13).) (In the above formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, phenylene, a sulfonyl group, or an amide group. ２ may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.) 5. The liquid crystal aligning agent according to claim 4, wherein the formula (x-1) is selected from the group consisting of the following formulas (x1-1) to (x1-6): (In the above formula, *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.) 6. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a diamine component containing at least one diamine selected from diamines represented by the following formula (3) or the following formula (3A): (In formula (3), Y ３ represents a divalent organic group represented by the following formula (O), and in formula (3A), Y ３ａ represents a divalent organic group represented by the following formula (a), where each of the multiple R's independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In formula (O), Ar represents a divalent benzene ring, biphenyl structure, naphthalene ring, or aromatic heterocycle. When a plurality of Ars are present, the two Ars may be the same 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. Q ３ Ha-(CH ２ ) ｎ -(n is an integer of 2 to 18), or the above-(CH ２ ) ｎ -of-CH ２ represents a group in which at least a portion of - has been replaced with either -O-, -C(=O)-, or -O-C(=O)-. * represents a bond. (In formula (a), a hydrogen atom on the benzene ring may be 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 a benzene ring or a biphenyl structure, and a hydrogen atom on the benzene ring or the biphenyl structure may be substituted with a methyl group or a fluorine atom. n is an integer of 0 to 5. When n is an integer of 2 or greater, the n Ps independently have the above definition. * represents a bond.) 7. The liquid crystal aligning agent according to claim 6, wherein the divalent organic group represented by formula (O) is any one of the following formulae (o-1) to (o-12): (In the formula, X １ , X ２ each independently represents a single bond or —O—. (In formula (o-7), X ７ Each independently represents a single bond or —O—. However, when n is 1, two X ７ At least one of represents —O—. In formula (o-12), two m's each independently have the above definition.

8. The liquid crystal aligning agent according to claim 3, wherein the polyimide precursor is obtained using a diamine component containing a diamine having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle (excluding imide rings contained in polyimides), a secondary amino group, and a tertiary amino group.

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

10. The liquid crystal aligning agent according to claim 1, further comprising at least one additive selected from the group consisting of an adhesion aid, a crosslinking compound, and a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film.

11. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 10 to a substrate, baking the applied film, and then subjecting the resulting film to an alignment treatment.

12. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 10.

13. A liquid crystal display device comprising the liquid crystal alignment film according to claim 12.

14. The liquid crystal display element according to claim 12, which is of an IPS drive system or an FFS drive system.

15. A compound represented by either formula (q1-3) or (q1-4): (Boc represents a tert-butoxycarbonyl group.)

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