Liquid crystal orientation agent, liquid crystal orientation film, liquid crystal display element, and method for manufacturing same

Abstract

Provided are a liquid crystal orientation agent, a liquid crystal orientation film, a liquid crystal display element, and a method for manufacturing the same, with which it is possible to obtain a liquid crystal orientation film that has excellent adhesion and that is capable of suppressing AC afterimages at a high level.　The liquid crystal orientation agent contains a polymer component (P) containing one or more types of polymer, and a compound (C1) and a compound (C2), the polymer component (P) containing at least one polymer (p) selected from the group consisting of a polyimide precursor and a polyimide that is an imidized product of the polyimide precursor. Compound (C1): a compound having two or more structures represented by any of formulae (c-1) to (c-1'). Compound (C2): a compound represented by any of formulae (c-2) to (c-2').

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing the same

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element.

[0002] A liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, pixel electrodes and a common electrode that apply an electric field to the liquid crystal layer, a liquid crystal alignment film that controls the orientation of liquid crystal molecules in the liquid crystal layer, thin film transistors (TFTs) that switch electric signals supplied to the pixel electrodes, etc. Known methods for driving liquid crystal molecules include vertical electric field methods such as the TN (Twisted Nematic) method and the VA (Vertical Alignment) method, and horizontal electric field methods such as the IPS (In-Plane Switching) method and the FFS (Fringe Field Switching) method.

[0003] Currently, the most widely used liquid crystal alignment films in industry are prepared by rubbing the surface of a film made of a polymer, typically polyamic acid and / or imidized polyimide, formed on an electrode substrate in one direction with a cloth made of cotton, nylon, polyester, or the like (see, for example, Patent Document 1). Rubbing is a simple, highly productive, and industrially useful method. Meanwhile, as liquid crystal display devices have become increasingly sophisticated, high-definition, and large, photoalignment methods, which impart liquid crystal alignment ability by irradiating the device with polarized radiation, have been proposed as alternative alignment methods to rubbing. Photoalignment methods utilizing photoisomerization, photocrosslinking, and photodecomposition have been proposed (see, for example, Patent Document 2 and Non-Patent Document 1). In recent years, the range of applications of liquid crystal display devices has expanded, and various properties are being sought for liquid crystal alignment films. For example, to ensure as large a display surface as possible, there is a demand for narrower frame widths of the sealant used to bond the substrates of liquid crystal display devices. Accordingly, liquid crystal alignment films that have high adhesiveness to sealing materials are required, and Patent Document 3 proposes a liquid crystal alignment agent that uses a crosslinking agent having a hydroxyalkylamide group.

[0004] Patent Document 1: WO2016 / 063834 Patent Document 2: Japanese Patent Application Laid-Open No. 2011-107266 Patent Document 3: WO2015 / 072554

[0005] "Liquid Crystal Photo-Alignment Film" Kidowaki, Ichimura Functional Materials, November 1997, Vol. 17, No. 11, pp. 13-22

[0006] On the other hand, liquid crystal alignment films used in liquid crystal display elements, such as those in the IPS mode and FFS mode, require a high alignment control force to suppress image retention (hereinafter also referred to as AC image retention) that occurs due to long-term AC driving. In recent years, large-screen, high-resolution liquid crystal display elements have become the norm, and the demand for higher quality liquid crystal display elements has increased more than ever before. As a result of the inventor's investigations, it has been found that conventional techniques cannot provide liquid crystal alignment films that satisfy these characteristics at a high level.

[0007] In view of the above, an object of the present invention is to provide a liquid crystal alignment agent capable of obtaining a liquid crystal alignment film that has excellent adhesion and can suppress AC afterimages to a high level, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element.

[0008] As a result of intensive research into achieving the above object, the present inventors have found that using a liquid crystal aligning agent containing a polymer component (P) containing one or more types of polymers and a specific compound component is extremely effective for achieving the above object, and have completed the present invention.

[0009] The present invention encompasses the following aspects. A liquid crystal aligning agent containing a polymer component (P) containing one or more types of polymer, a compound (C1), and a compound (C2), wherein the polymer component (P) contains at least one polymer (p) selected from the group consisting of polyimide precursors and polyimides that are imidized products of the polyimide precursors. Compound (C1): A compound having two or more structures represented by any one of the following formulas (c-1) to (c-1'). Compound (C2): A compound represented by any one of the following formulas (c-2) to (c-2').

[0010] (In formula (c-1), R ２ and R ２’are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group "*3-CH ２ -O-R １１ ” (R １１ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ and R ２’ represents a bond to the carbon atom to which it is bonded. ３ and R ３’ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. *1 and *2 represent a bond. n1 represents an integer of 0 or 1. In formula (c-2), a is an integer of 2 to 4, Ra is an a-valent organic group, and the bonding sites to the a N atoms are aliphatic carbon atoms or aromatic carbon atoms. In formula (c-1'), R ４２ and R ４２ ' are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group "*43-CH ２ -O-R ４１ ” (R ４１ represents a monovalent group having a tetrahydropyran ring structure or an alkyl group having 1 to 3 carbon atoms. ４２ and R ４２’ represents a bond to the carbon atom to which it is bonded. ４３ and R ４３ Each of the symbols ' independently represents a hydrogen atom, a monovalent group having a tetrahydropyran ring structure, or an alkyl group having 1 to 3 carbon atoms. n41 represents an integer of 0 or 1. Dx represents a monovalent group having a tetrahydropyran ring structure. *1 and *2 are synonymous with *1 and *2 in formula (c-1). In formula (c-2'), c1 is an integer of 1 to 6, Rc is a c2-valent organic group, and the bonding site to the oxygen atom is an aliphatic carbon atom or an aromatic carbon atom. c2 is an integer of 3 to 4.) Throughout this specification, the following terms and abbreviations have the following meanings: A halogen atom is a fluorine atom, chlorine atom, bromine atom, iodine atom, etc. In both cases, * represents a bond. Furthermore, Boc represents a tert-butoxycarbonyl group, and Fmoc represents a 9-fluorenylmethoxycarbonyl group.

[0011] According to the present invention, it is possible to obtain a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film that has excellent adhesion and can suppress AC afterimages to a high level, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element. The mechanism by which the above-mentioned effects of the present invention are obtained is not necessarily clear, but it is roughly presumed as follows. A compound with a high cross-linking reaction rate on the polyimide film surface can obtain a liquid crystal alignment film with excellent adhesion. On the other hand, a compound with a low cross-linking reaction rate on the polyimide film surface can increase the film hardness of the liquid crystal alignment film without inhibiting the alignment of the liquid crystal. Therefore, it is thought that the above-mentioned effects were obtained by mixing the two.

[0012] FIG. 1 is a simplified diagram of a test sample substrate used in evaluating adhesion between a sealant and an underlying substrate.

[0013] <Polymer component (P)> The polymer component (P) contained in the liquid crystal aligning agent of the present invention contains at least one polymer (p) selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors. The polymer (p) has, for example, one or more structural units, and may have at least one structural unit selected from the group consisting of a structural unit (p0) represented by the following formula (P0) and an imidized structural unit of the structural unit (p0). (In formula (P0), X represents a tetravalent organic group, Y represents a divalent organic group, R and Z each independently represent a hydrogen atom or a monovalent organic group, and multiple R's and Z's each independently have the above definition.)

[0014] X in the formula (P0) represents a tetravalent organic group, preferably a tetravalent tetracarboxylic acid residue. Here, the tetravalent tetracarboxylic acid residue may be, for example, a tetravalent organic group present among four carbonyl groups of a tetracarboxylic acid dianhydride or a derivative thereof (e.g., a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide). From the viewpoint of optimally achieving the effects of the present invention, X is preferably a tetravalent tetracarboxylic acid residue derived from an acyclic aliphatic tetracarboxylic acid dianhydride, an alicyclic tetracarboxylic acid dianhydride, an aromatic tetracarboxylic acid dianhydride, or a derivative thereof. The tetracarboxylic acid dianhydride or a derivative thereof that provides X is preferably a tetracarboxylic acid dianhydride or a derivative thereof having at least one structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. Here, the acyclic aliphatic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed solely of a chain hydrocarbon structure, and it may have an alicyclic structure or an aromatic ring structure as part of it. An alicyclic tetracarboxylic acid dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to the alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, it does not have to be composed solely of an alicyclic structure, and it may have a chain hydrocarbon structure or an aromatic ring structure as part of it. An 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. However, it does not have to be composed solely of an aromatic ring structure, and it may have a chain hydrocarbon structure or an alicyclic structure as part of it.

[0015] In order to preferably obtain the effects of the present invention, X in the above formula (P0) is any one of the following formulae (Xa1-1) to (Xa1-8), the following formulae (X-1) to (X-17), or the following formula (X ｂ１ -a) to (X ｂ１-c) is a tetravalent organic group. (In formulas (Xa1-1) to (Xa1-3), R １ From R １５ 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 containing a fluorine atom, or a phenyl group, and may be the same or different. * represents a bond.) (x and y each independently represent a single bond, an ether, a carbonyl, an ester, an alkanediyl group having 1 to 10 carbon atoms, 1,4-phenylene, a sulfonyl, or an amide bond; j and k each represent 0 or 1.)

[0016] R in the above formulas (Xa1-1) to (Xa1-3) １ ~R １５ Specific examples of the alkyl group having 1 to 6 carbon atoms in the above R include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. １ ~R １５ Specific examples of the alkenyl group having 2 to 6 carbon atoms in the above R include a vinyl group, a propenyl group, and a butenyl group, which may be linear or branched. １ ~R １５ Specific examples of the alkynyl group having 2 to 6 carbon atoms in the above R include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, and a 3-butynyl group. １ ~R １５ In the formula (I), examples of the monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom include a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, and a pentafluoropropyl group. ａ１ is preferably a tetravalent organic group represented by the above formula (Xa1-1). １ ~R ４ are each independently a hydrogen atom or a methyl group, and R １~R ４ Preferably, at least one of R is a methyl group. １ ~R ４ It is more preferable that at least two of R are methyl groups. １ and R ４ is a methyl group, and R ２ and R ３ is a hydrogen atom. The above formula (Xa1-1) is preferably a tetravalent organic group selected from the group consisting of the following formulae (Xa1-1-1) to (Xa1-1-5):

[0017] The above formula (X ｂ１ -a) to (X ｂ１ From the viewpoint of suitably obtaining the effects of the present invention, the tetravalent organic group represented by any one of the following formulas (X ｂ１ -1) to (X ｂ１ -21) is more preferred.

[0018] The divalent organic group for Y in the above formula (P0) is not particularly limited, but examples thereof include divalent organic groups represented by any of the following formulae (3) and (4). (In formulas (3) and (4), R ３ , R ４ , and R ４’ A each independently represents a halogen atom, a hydroxy group, an optionally protected amino group, a thiol group, a nitro group, a phosphate group, or a monovalent organic group having 1 to 20 carbon atoms. ４ represents an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 20 carbon atoms, provided that 1,4-phenylene group, 1 to 4 of the hydrogen atoms on the phenylene group are R ４ , and R ４’ a3, a4, and a4' are each independently an integer of 0 to 4. a is an integer of 1 to 4. b and c are each independently an integer of 1 or 2. R ３ , R ４ , R ４’ If there are multiple R３ , R ４ , and R ４’ The structures of may be the same or different. When a plurality of a3, a4, and a4' are present, they may be the same or different. * represents a bond.

[0019] R in the above formulas (3) and (4) ３ , R ４ , and R ４’ In the above formula, the monovalent organic group having 1 to 20 carbon atoms includes a monovalent hydrocarbon group having 1 to 20 carbon atoms, and any methylene group of the hydrocarbon group can be replaced with -O-, -S-, -C(=O)-, -C(=O)-O-, -C(=O)-S-, -NR ３ - (However, R ３ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a tert-butoxycarbonyl group; ３ - (However, R ３ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a tert-butoxycarbonyl group.), —Si(R ３ ) ２ - (However, R ３ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms; —S(═O) ２ - or the like (hereinafter, these groups are also referred to as heteroatom-containing groups (A)), a monovalent group (A2) in which at least one hydrogen atom bonded to a carbon atom of a monovalent hydrocarbon group or a monovalent group A is substituted with a halogen atom, a hydroxy group, an alkoxy group, a nitro group, an amino group which may be protected by a protecting group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, an acyl group, or the like, and a monovalent group having a heterocycle. The number of carbon atoms in the group (A), the group (A2), and the monovalent group having a heterocycle is 1 to 20. ３ , R ４ , and R ４’As the monovalent organic group having 1 to 20 carbon atoms in the above, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a monovalent group obtained by replacing any methylene group of the hydrocarbon group with the heteroatom-containing group (A) are more preferred. ２ and R represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a tert-butoxycarbonyl group. ３ , R ４ , and R ４’ The monovalent organic group having 1 to 20 carbon atoms in the formula (I) is preferably a methyl group, a methoxy group, a vinyl group, a halogen atom, a hydroxy group, an amino group which may be protected by a protecting group, or a monovalent group in which at least one hydrogen atom of an alkyl group having 1 to 3 carbon atoms has been substituted with a halogen atom or an amino group which may be protected by a protecting group.

[0020] In the above formula (3), a is preferably an integer of 1 or 2. In the above formula (3), a3 is preferably an integer of 0 to 2, and when there are multiple a3s, they may be the same or different. In the above formula (4), a4 and a4' are each independently preferably an integer of 0 to 2, and when there are multiple a4s and multiple a4's, they may be the same or different.

[0021] A in the above formula (4) ４ The divalent organic group having 2 to 20 carbon atoms in the formula (I) includes a hydrocarbon group having 2 to 20 carbon atoms; any alkylene group contained in the hydrocarbon group can be selected from the group consisting of -C(=O)-, -NR-, -C(=O)-O-, -Si(R ０ ) ２and -O-C(=O)- (4a) (wherein the carbon number of the divalent organic group (4a) is 2 to 20); a divalent organic group (4b) in which -O- is inserted at least one position between the terminal of a hydrocarbon group having 2 to 20 carbon atoms and between the carbon-carbon bonds of any alkylene groups contained in the hydrocarbon group; a divalent organic group (4c) in which -O- is inserted at least one position between the carbon-carbon bonds of any alkylene groups contained in the divalent organic group (4a); a divalent organic group (4d) having 2 to 20 carbon atoms and having a heterocyclic ring; and the like. In the above -NR-, R represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, or a tert-butoxycarbonyl group. The above -Si(R ０ ) ２ R in - ０ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0022] Examples of the hydrocarbon group include a chain hydrocarbon group, an alicyclic hydrocarbon group, or a hydrocarbon group having an aromatic group (examples of the aromatic ring structure in the aromatic group include a benzene ring, a naphthalene ring, a biphenyl structure, an anthracene ring, etc.). Specific examples of the chain hydrocarbon group include a divalent, straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms without a cyclic structure, and are preferably an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or an alkynylene group having 2 to 20 carbon atoms. Specific examples of the alicyclic hydrocarbon group include an alicyclic structure (e.g., a cyclohexylene group or a bicyclohexylene group), or a hydrocarbon group having an alicyclic structure and a chain hydrocarbon structure. Specific examples of the hydrocarbon group having an aromatic group include an aromatic group, a hydrocarbon group having an aromatic group and a chain hydrocarbon structure, a hydrocarbon group having an aromatic group and an alicyclic structure, etc.

[0023] Examples of the heterocyclic ring in the divalent organic group (4d) include a piperidine ring, a piperazine ring, a morpholine ring, a pyrrolidine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an imide ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring, or a fused ring containing such a ring structure as a part of its structure, and the hydrogen atoms on the ring may be substituted. Examples of the substituent include a halogen atom, a methyl group, or a methoxy group.

[0024] A in the above formula (4) ４ From the viewpoint of suitably obtaining the effects of the present invention, １ -A-L １’ -" or a divalent organic group having 2 to 20 carbon atoms and a heterocyclic ring is preferred. １ -A-L １’ L in "-" １ , L １’ The total number of carbon atoms in L and A is 2 to 20. １ and L １’ each independently represents a single bond, —O—, —NR—, —C(═O)—NR—, —C(═O)—, or —O—C(═O)—, and R represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, or a tert-butoxycarbonyl group. １ -A-L １’ In order to obtain the effects of the present invention, A in "-" is an alkylene group having 1 to 12 carbon atoms, -CH=CH-, -C≡C-, -CR ０ =CR ０’ -C(=O)-O-(R ０ and R ０’ each independently represents a hydrogen atom or a methyl group, or —O—, —NR—, —C(═O)—NR—, —C(═O)—NR—C(═O)—, —C(═O)—O—, —Si(R ａ ) ２ represents a divalent organic group into which at least one group of - and -O-C(=O)- is inserted, such as -O-Ar-O-, -O-C(=O)-Ar-C(=O)-O-, or -C(=O)-O-Ar-O-C(=O)-.１ and L １’ represents a single bond, A represents a group other than a methylene group. R in the above -C(=O)-NR- and -C(=O)-NR-C(=O)- represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, or a tert-butoxycarbonyl group. -Si(R ａ ) ２ R in - ａ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 3 carbon atoms. Any hydrogen atom possessed by A may be substituted with a halogen atom. Ar in the above -O-Ar-O-, -O-C(=O)-Ar-C(=O)-O-, and -C(=O)-O-Ar-O-C(=O)- represents a phenylene group or a biphenyl structure.

[0025] More preferred examples of the above formulas (3) and (4) include the following formula (d ＡＬ -1) to (d ＡＬ -12), (5-1) to (5-6), (z-1) to (z-7), (o2-1) to (o2-12), (h-1) to (h-13) and (Im-1) to (Im-6), (d Ｂｚ -1) to (d Ｂｚ The structure represented by the following formula (d ＡＬ -1) to (d ＡＬ In the structure represented by any one of (5-8), (5-1) to (5-6), (z-1) to (z-7), (o2-1) to (o2-12), and (h-1) to (h-13), the bonding positions of the benzene ring bonded to * are the 1,4-positions. ＡＬ In formula (9), all of the benzene rings are bonded at the 1,4-positions.

[0026] (Formula (d ＡＬ In formula (d-6), when m1 and m2 are 0, the sum of m1, m2 and n is 1 to 12, and when at least one of m1 and m2 is an integer other than 0, the sum of m1, m2 and n is 2 to 12. ＡＬ In formula (d-8), the sum of m1, m2 and n is 3 to 12. ＡＬ -11) and formula (d ＡＬ -12), the sum of m1, m2 and n is 3 to 12.

[0027] From the viewpoint of suitably achieving the effects of the present invention, the polymer (p) is preferably a polymer containing a structural unit having a divalent organic group selected from the group consisting of a divalent organic group having a urea bond; a divalent organic group having an amide bond; a divalent organic group having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group; and a divalent organic group having a carboxy group (these are also collectively referred to as the specific divalent organic group (b)).

[0028] Examples of the divalent organic group having a urea bond include A in the above formula (4). ４ The divalent organic group having an amide bond is represented by the formula (4) above, in which A has the group "-NH-C(=O)-NR-". ４Examples of the divalent organic group having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group include 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, and divalent organic groups having a structure represented by any one of the above formulas (z-1) to (z-7). and diamines having a diphenylamine structure typified by 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N'-dimethylbenzidine, or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine; and divalent organic groups obtained by removing two amino groups from a diamine selected from the group consisting of: Examples of the divalent organic group having a carboxy group include divalent organic groups obtained by removing two amino groups from a diamine having a carboxy group, such as 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 1,2-bis(4-aminophenyl)ethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid.

[0029] In addition, Y in the above formula (A1) ａ１The divalent organic group may have a structure other than the divalent organic group represented by any one of the formulas (3) to (4). Examples of such a structure include a divalent organic group (3L) in which the bonding position of the benzene ring bonded to * in the formula (3) is changed from the 1,4-position to the 2,5-position; a divalent organic group (4L) in which at least one bonding position of the benzene ring bonded to * in the formula (4) is changed from the 1,4-position to the 2,5-position; or a divalent organic group obtained by removing two amino groups from the following diamine (the diamines are also collectively referred to as diamine (W)). In the divalent organic groups (3L) and (4L), R ３ , R ４ , R ４’ , A ４ , a3, a4, a4', a, b, and c have the same meanings as those in the formulas (3) and (4).

[0030] aromatic diamines having a naphthalene ring such as 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, or 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4,4'-diaminoazobenzene, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, Diaminobenzophenone, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)- compounds having a steroid skeleton such as 1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestanyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane; diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO2018 / 117239.

[0031] From the viewpoint of suitably achieving the effects of the present invention, the polymer (p) preferably contains the structural unit (p0) and the imidized structural units of the structural unit (p0) in a total amount of 10 to 100 mol %, more preferably 15 to 100 mol %, of all structural units contained in the polymer (p). Note that this total also includes cases where either the structural unit (p0) or the imidized structural units of the structural unit (p0) is 0 mol %. Hereinafter, the term "total" also includes cases where one or more of the structural unit elements are 0 mol %.

[0032] From the viewpoint of suitably obtaining the effects of the present invention, the polymer (p) preferably contains structural units having a divalent organic group represented by any one of the above formulas (3) and (4) in an amount of 10 to 100 mol %, more preferably 15 to 100 mol %, of all structural units contained in the polymer (p).

[0033] The monovalent organic groups for R and Z in the formula (P0) include monovalent hydrocarbon groups having 1 to 20 carbon atoms, and methylene groups of the hydrocarbon groups may be substituted with -O-, -S-, -CO-, -COO-, -COS-, -NR ３ --CO-NR ３ -, -Si(R ３ ) ２ -, -SO ２ - or the like (wherein R ３ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ３ If there are multiple R ３may be the same or different. ) Examples include monovalent groups in which at least one hydrogen atom bonded to a carbon atom of such a monovalent hydrocarbon group or monovalent group A is substituted with a halogen atom, a hydroxy group, an alkoxy group, a nitro group, an amino group, a mercapto group, a nitroso group, an alkylsilyl group, an alkoxysilyl group, a silanol group, a sulfino group, a phosphino group, a carboxy group, a cyano group, a sulfo group, an acyl group, or the like, and monovalent groups having a heterocycle. The monovalent organic groups represented by R and Z in formula (P0) above are preferably alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, Boc, or Fmoc, more preferably alkyl groups having 1 to 3 carbon atoms, and even more preferably methyl groups. From the viewpoint of suitably achieving the effects of the present invention, R and Z are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0034] The polymer component (P) contained in the liquid crystal aligning agent of the present invention may be a polymer component containing two or more polymers and satisfying at least one of the following conditions (i) to (iii): (i) polymer component (P1) containing two or more polymers selected from the group consisting of polyimide precursors (A) having one or more structural units and having a structural unit (a1) represented by the following formula (A1) and polyimides which are imidized products of the polyimide precursors; (ii) polymer component (P2) containing two or more polyimide precursors (B) which are different from the polyimide precursor (A), have one or more structural units and have a structural unit (b1) represented by the following formula (B1); and (iii) polymer component (P3) containing the polyimide precursor (B) and at least one polymer selected from the group consisting of the polyimide precursors (A) and polyimides which are imidized products of the polyimide precursors. (In formula (A1), X ａ１ represents a tetravalent organic group selected from the group consisting of the above formulae (Xa1-1) to (Xa1-8), Y ａ１ represents a divalent organic group. In the above formula (A1), R and Z have the same meanings as in the above formula (P0). (In formula (B1), Xｂ１ represents a tetravalent organic group having an aromatic group having 6 to 30 carbon atoms; X ｂ１ At least one of the carbonyl carbons bonded to X ｂ１ It bonds to the aromatic group of Y. ｂ１ represents a divalent organic group. In the above formula (B1), R and Z have the same meanings as in the above formula (P0).

[0035] The polymer component (P) may be composed of a polymer that does not have an acid-dissociable group. Here, the acid-dissociable group is a group having a bond that is cleaved by acid, and upon cleavage of the bond, some or all of the acid-dissociable group is dissociated from the main chain of the polymer. Preferred examples of the acid-dissociable group include protecting groups that protect amino groups, hydroxy groups, and the like. Examples of such protecting groups include carbamate-based protecting groups (specific examples include tert-butoxycarbonyl and 9-fluorenylmethyloxycarbonyl), and groups that form an acetal structure or a tertiary ether structure together with the protected oxygen atom. A polymer that does not have an acid-dissociable group can be obtained, for example, by using a raw material component that does not have an acid-dissociable group (specific examples of raw materials that do not have an acid-dissociable group include a diamine that does not have an acid-dissociable group, a tetracarboxylic dianhydride or a derivative thereof that does not have an acid-dissociable group, and a terminal modifier that does not form an acid-dissociable group).

[0036] <Polyimide precursor (A)> The polymer components (P1) and (P3) contained in the liquid crystal aligning agent of the present invention contain a polyimide precursor (A) having one or more structural units and having a structural unit (a1) represented by the above formula (A1). The polyimide precursor (A) may be one or more polymers. The polyimide precursor (A) may have one type of structural unit, two or more different structural units, three or more different structural units, or four or more different structural units.

[0037] Y in the above formula (A1) ａ１The divalent organic group is not particularly limited, and examples thereof include divalent organic groups represented by any one of the above formulas (3) to (4). The divalent organic group is introduced into the structural unit of the polyimide precursor (A), for example, by using a diamine having the above divalent organic group as the diamine component for obtaining the polyimide precursor (A). From the viewpoint of suitably achieving the effects of the present invention, at least one of the structural units constituting the polyimide precursor (A) preferably has a structure selected from the group consisting of divalent organic groups represented by any one of the above formulas (3) to (4), and more preferably has a structure selected from the group consisting of divalent organic groups represented by any one of the above formulas (3) to (4) in which * is bonded to a nitrogen atom derived from the diamine. Furthermore, from the viewpoint of suitably achieving the effects of the present invention, in the above formula (A1), Y ａ１ is preferably a divalent organic group selected from the group consisting of the above formulas (3) and (4).

[0038] More preferred examples of the formulas (3) and (4) are the same as the preferred embodiments of the formulas (3) to (4) in the polymer (p). Among them, more preferred examples include the formula (d ＡＬ -1) to (d ＡＬ Examples of the structure include those represented by any one of the formulas (d ＡＬ -1) to (d ＡＬ In the structure represented by any one of (5-8), (5-1) to (5-6), (z-1) to (z-7), (o2-1) to (o2-12), and (h-1) to (h-13), the bonding positions of the benzene ring bonded to * are the 1,4-positions. ＡＬ In formula (9), all of the benzene rings are bonded at the 1,4-positions.

[0039] In addition, Y in the above formula (A1) ａ１The divalent organic group may have a structure other than the divalent organic group represented by any one of the formulas (3) to (4). Examples of such a structure include a divalent organic group (3L) in which the bonding position of the benzene ring bonded to * in the formula (3) is changed from the 1,4-position to the 2,5-position; a divalent organic group (4L) in which at least one bonding position of the benzene ring bonded to * in the formula (4) is changed from the 1,4-position to the 2,5-position; or a divalent organic group obtained by removing two amino groups from the diamine (W). In the divalent organic groups (3L) and (4L), R ３ , R ４ , R ４’ , A ４ , a3, a4, a4', a, b, and c have the same meanings as those in the formulas (3) and (4).

[0040] From the viewpoint of suitably achieving the effects of the present invention, the polyimide precursor (A) may be a polyimide precursor having, in addition to the structural unit (a1) represented by the above formula (A1), a structural unit (a2) represented by the following formula (A2): (In formula (A2), X ａ２ represents a tetravalent organic group represented by any one of the above formulas (X-1) to (X-17) or a tetravalent organic group derived from an aromatic tetracarboxylic dianhydride, Y ａ２ represents a divalent organic group. In the above formula (A2), R and Z have the same meanings as in the above formula (P0).

[0041] Y in the above formula (A2) ａ２ Specific examples of the divalent organic group include Y in the above formula (A1). ａ１ Examples of the divalent organic group include the structures exemplified above, including preferred embodiments.

[0042] The aromatic tetracarboxylic dianhydride is as defined above, including preferred embodiments. Specific preferred examples of the aromatic tetracarboxylic dianhydride include those represented by the above formula (X ｂ１ -a) to (X ｂ１ -c), and more preferably, ｂ１ -1) to (X ｂ１-21).

[0043] From the viewpoint of optimally achieving the effects of the present invention, the polyimide precursor (A) preferably contains 10 to 100 mol %, more preferably 15 to 100 mol %, of the total structural units contained in the polyimide precursor (A) of the structural unit (a1) and the imidized structural units of the structural unit (p0). From the viewpoint of optimally achieving the effects of the present invention, the polyimide precursor (A) preferably contains 10 to 100 mol %, more preferably 15 to 100 mol %, of the total structural units contained in the polyimide precursor (A) of structural units having a divalent organic group represented by any one of the above formulas (3) to (4). When the polyimide precursor (A) contains structural units other than the structural unit (a1) and / or the imidized structural units of the repeating unit (a1), the total of the structural unit (a1) and the imidized structural units of the structural unit (a1) preferably constitutes 95 mol % or less, more preferably 90 mol % or less, of the total structural units contained in the polyimide precursor (A).

[0044] <Polyimide precursor (B)> The polymer components (P2) and (P3) contained in the liquid crystal aligning agent of the present invention contain a polyimide precursor (B), which is a polymer different from the polyimide precursor (A) and has one or more structural units, including a structural unit (b1) represented by the following formula (B1). One or more types of polymers may be used as the polyimide precursor (B). The polyimide precursor (B) may have one type of structural unit, or two or more different types of structural units, or three or more different types of structural units, or four or more different types of structural units. (In formula (B1), X ｂ１ represents a tetravalent organic group having an aromatic group having 6 to 30 carbon atoms; X ｂ１ At least one of the carbonyl carbons bonded to X ｂ１ It bonds to the aromatic group of Y. ｂ１ represents a divalent organic group. In the above formula (B1), R and Z have the same meanings as in the above formula (P0).

[0045] X in the above formula (B1) ｂ１represents a tetravalent organic group having an aromatic group having 6 to 30 carbon atoms; X ｂ１ At least one of the carbonyl carbons bonded to X ｂ１ More preferably, it is a tetravalent organic group derived from an acid dianhydride obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring (such as a benzene ring or a naphthalene ring). However, it is not necessary for the group to be composed of only an aromatic ring structure, and it may also have a chain hydrocarbon structure or an alicyclic structure as part of it. X ｂ１ A preferred example of X is a tetravalent organic group derived from an aromatic tetracarboxylic acid compound. ｂ１ is preferably represented by the above formula (X ｂ１ -a) to (X ｂ１ -c), and more preferably, a tetravalent organic group represented by the above formula (X ｂ１ -1) to (X ｂ１ -21), and more preferably, a tetravalent organic group represented by the above formula (X ｂ１ -1) to (X ｂ１ A tetravalent organic group represented by any one of the formulas (X-13) is more preferred. ｂ１ -1) to (X ｂ１ -7).

[0046] Above Y ｂ１ The divalent organic group in ａ１ In order to obtain the effects of the present invention, the polyimide precursor (B) is preferably a polymer containing a structural unit having the specific divalent organic group (b). In addition, in order to obtain the effects of the present invention, the polyimide precursor (B) is preferably a polymer containing a structural unit having the specific divalent organic group (b) described above. ｂ１ is preferably a polymer containing a structural unit which is the specific divalent organic group (b) described above.

[0047] From the viewpoint of suitably obtaining the effects of the present invention, the polyimide precursor (B) preferably contains structural units having the specific divalent organic group (b) (more preferably structural units having the specific divalent organic group bonded to a nitrogen atom derived from a diamine) in an amount of 1 mol % or more, preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more of the total structural units contained in the polyimide precursor (B). ｂ１ is the specific divalent organic group (b) in an amount of 1 mol % or more, preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more of all structural units contained in the polyimide precursor (B).

[0048] From the viewpoint of suitably achieving the effects of the present invention, the polyimide precursor (B) may be a polyimide precursor having, in addition to the structural unit (b1) represented by the above formula (B1), a structural unit (b2) represented by the following formula (B2): (In formula (B2), X ｂ２ represents a tetravalent organic group derived from an acyclic aliphatic tetracarboxylic acid dianhydride or an alicyclic tetracarboxylic acid dianhydride; Y ｂ２ represents a divalent organic group. In the above formula (B2), R and Z have the same meanings as in the above formula (P0).

[0049] In the formula (B2), the acyclic aliphatic tetracarboxylic acid dianhydride and the alicyclic tetracarboxylic acid dianhydride are as defined above.

[0050] X ｂ２ From the viewpoint of suitably achieving the effects of the present invention, Y in the above formula (B2) is preferably a tetravalent organic group represented by any one of the above formulas (X-1) to (X-17) or (Xa1-1) to (Xa1-8). ｂ２ Specific examples of the divalent organic group include Y in the above formula (B1). ｂ１ Examples of the divalent organic group include the structures exemplified above, including preferred embodiments.

[0051] From the viewpoint of optimally achieving the effects of the present invention, the polyimide precursor (B) preferably contains the structural unit (b1) and the imidized structural unit of the structural unit (p0) in a total amount of 10 to 100 mol%, more preferably 15 to 100 mol%, of the total structural units contained in the polyimide precursor (B). Furthermore, when the polyimide precursor (B) contains structural units other than the structural unit (b1) and / or the imidized structural unit of the repeating unit (b1), the structural unit (b1) preferably accounts for 95 mol% or less, more preferably 90 mol% or less, of the total structural units contained in the polyimide precursor (B). The polyimide precursor (B) preferably contains the structural unit (b2) in an amount of 5 mol% or more, more preferably 10 mol% or more, of the total structural units contained in the polyimide precursor (B). Furthermore, the structural unit (b2) preferably accounts for 90 mol% or less, more preferably 85 mol% or less, of the total structural units contained in the polyimide precursor (B).

[0052] In the polymer component (P), the mass ratio of the content of the first polyimide precursor to the content of the second polyimide precursor (content of the first polyimide precursor / content of the second polyimide precursor) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 90 / 10, and even more preferably 20 / 80 to 80 / 20. From the viewpoint of reducing afterimages resulting from residual DC, the mass ratio of the content of the polyimide precursor (A) to the content of the polyimide precursor (B) (content of the polyimide precursor (A) / content of the polyimide precursor (B)) is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 90 / 10, and even more preferably 20 / 80 to 80 / 20.

[0053] <Method for Producing Polymer (p), Polyimide Precursor (A), and Polyimide Precursor (B)> The polymer (p) and polyimide precursors (A) and (B) in the present invention can be synthesized by a known method such as that described in WO2013 / 157586.

[0054] Specifically, it can be obtained by reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid dianhydride with a diamine component in a solvent (condensation polymerization). The solvent is not particularly limited as long as it dissolves the produced polymer.

[0055] For example, when synthesizing a polyimide precursor (A) having a repeating unit represented by the above formula (A1), the diamine component may be -NZ-Y ａ１ -NZ- structure (Y ａ１ , Z is Y in formula (A1) ａ１ The tetracarboxylic acid derivative component is a diamine having the above formula (X ａ１ ) structure (X ａ１ is X in formula (A1) ａ１ The tetracarboxylic dianhydride having the same definition as that of the tetracarboxylic dianhydride having the same meaning ...

[0056] The ratio of tetracarboxylic dianhydride and diamine used in the polyimide precursor synthesis reaction is preferably such that 0.5 to 2 equivalents of the acid anhydride groups of the tetracarboxylic dianhydride are used per equivalent of the amino groups of the diamine, more preferably 0.8 to 1.2 equivalents. As with conventional polycondensation reactions, the closer the equivalent of the acid anhydride groups of the tetracarboxylic dianhydride is to 1 equivalent, the higher the molecular weight of the resulting polyimide precursor. The reaction temperature in the polyimide precursor synthesis reaction is preferably −20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The polyimide precursor synthesis reaction can be carried out at any concentration, but the concentration of the polyimide precursor in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, with subsequent addition of solvent.

[0057] Specific examples of the solvent used when reacting the diamine component with the tetracarboxylic acid derivative component include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or H ３ C-CH(OH)-CH ２ -O-D１ (D １ represents an alkyl group having 1 to 3 carbon atoms, HO—CH ２ -CH ２ -O-D ２ (D ２ represents an alkyl group having 1 to 3 carbon atoms, HO—CH ２ -CH ２ -O-CH ２ -CH ２ -D ３ (D ３ represents an alkyl group having 1 to 4 carbon atoms.) These solvents may be used alone or in combination.

[0058] The above H ３ C-CH(OH)-CH ２ -O-D １ , HO-CH ２ -CH ２ -O-D ２ , HO-CH ２ -CH ２ -O-CH ２ -CH ２ -D ３ Specific examples of the solvent represented by the formula (I) include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

[0059] <Solution Viscosity and Molecular Weight of Polymer> In the present invention, the polymer (p), polyimide precursor (A), and polyimide precursor (B) preferably have a solution viscosity of, for example, 10 to 1,000 mPa s when made into a solution of 10 to 15 mass % 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 mass % prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0060] The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (p), polyimide precursor (A), and polyimide precursor (B) measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, more preferably 10 or less. A molecular weight within this range is preferred from the viewpoint of optimally achieving the effects of the present invention.

[0061] <End-capping agent> When synthesizing the polymer (p), polyimide precursor (A), and polyimide precursor (B) of the present invention, a suitable end-capping agent may be used together with the above-mentioned tetracarboxylic acid derivative component and diamine component to form an end-capping type polymer. The end-capping type polymer has the effect of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion properties between the sealant and the liquid crystal alignment film.

[0062] Examples of the terminals of the polymer (p), polyimide precursor (A), and polyimide precursor (B) in the present invention include an amino group, a carboxy group, an acid anhydride group, or a derivative thereof. The amino group, carboxy group, and acid anhydride group can be obtained by a conventional condensation reaction or by blocking the terminals with the following terminal blocking agents, for example, they can be obtained in the same manner using the following terminal blocking agents.

[0063] Examples of the end-capping agent include acid monoanhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4 ... monoamine compounds such as 5-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; monoisocyanate compounds such as isocyanates having an unsaturated bond, such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, and 2-methacryloyloxyethyl isocyanate; and isothiocyanate compounds such as ethyl isothiocyanate and allyl isothiocyanate.

[0064] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0065] <Compound (C1) and Compound (C2)> The liquid crystal aligning agent of the present invention contains the above-mentioned compound (C1) and compound (C2). The contents of the compound (C1) and compound (C2) used in the present invention are each independently preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymer component (P) contained in the liquid crystal aligning agent. The compound (C1) and compound (C2) can be used alone or in combination of two or more.

[0066] (Compound (C1)) From the viewpoint of suitably achieving the effects of the present invention, the molecular weight of the compound (C1) is more preferably 2000 or less, and preferably 150 or more. Furthermore, the molecular weight is further preferably 200 to 1800, and even more preferably 200 to 1500.

[0067] R ４１ , R ４２ , R ４２’ , R ４３ , R ４３’ Examples of the monovalent group having a tetrahydropyran ring structure in Dx include structures represented by any of the following formulae (Dx-1) to (Dx-4), with the structure represented by formula (Dx-1) being preferred. (* represents a bond.)

[0068] The compound (C1) is more preferably a compound represented by any one of the following formulas (1c-1) to (1c-4).

[0069] (In formulas (1c-1) to (1c-3), W represents an n-valent organic group (n represents an integer of 2 to 6). R １ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ —OH(n1, R ２ , R ２’ , R ３ , R ３’ has the same meaning as in formula (c-1). ２、 R ３、 R ２’ and R ３’ has the same definition as in formula (c-1). ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ —OH(n1, R ２ , R ２’ , R ３ , R ３’has the same definition as in formula (c-1). ４ and R ５ At least two of the following are -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ In formula (1c-4), W represents —OH. ４ represents an n-valent organic group (n ４０ represents an integer of 2 to 6.) R ４１ , R ４２ , R ４２’ , R ４３ , R ４３’ , Dx and n41 are defined as in formula (c-1').

[0070] Examples of the n-valent organic group include an n-valent hydrocarbon group, an n-valent heteroatom-containing group containing a group having a heteroatom at least on one of the carbon-carbon bonds of the hydrocarbon group and the terminal of the hydrocarbon group, an n-valent group in which some or all of the hydrogen atoms of the hydrocarbon group and the heteroatom-containing group are substituted with substituents, a divalent heterocycle, or a divalent organic group in which these divalent heterocycles are linked by a single bond, etc. Examples of the heterocycle include aromatic heterocycles such as a pyridine ring and a piperidine ring; and aliphatic heterocycles such as a piperidine ring and a piperazine ring.

[0071] Examples of n-valent hydrocarbon groups include chain hydrocarbons having 1 to 30 carbon atoms, such as alkanes such as methane, ethane, propane, and butane; alkenes such as ethylene, propylene, butylene, and pentene; and alkynes such as ethyne, propyne, butyne, and pentyne; alicyclic hydrocarbons having 3 to 30 carbon atoms, such as cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, and adamantane; cycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, and norbornene; and aromatic hydrocarbons having 6 to 30 carbon atoms, such as benzene, toluene, xylene, mesitylene, naphthalene, methylnaphthalene, dimethylnaphthalene, and anthracene. However, the chain hydrocarbons do not necessarily have to be composed solely of chain hydrocarbons, and may contain alicyclic hydrocarbons or aromatic hydrocarbons as part of them.

[0072] Examples of groups having a heteroatom include groups having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a phosphorus atom, and a sulfur atom, and examples thereof include -O-, -NR- (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, and groups combining these (-O-CO-, -NR-CO-, -NR-CO-NR-, etc.), heterocycles, or divalent organic groups in which these divalent heterocycles are linked by a single bond. Specific examples of such heterocycles include the structures exemplified above for the divalent heterocycles.

[0073] Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group; alkoxycarbonyl groups such as a methoxycarbonyl group and an ethoxycarbonyl group; alkoxycarbonyloxy groups such as a methoxycarbonyloxy group and an ethoxycarbonyloxy group; a cyano group, and a nitro group.

[0074] Preferred examples of the compound having the structure represented by formula (c-1) are compounds represented by any of the following formulas (c1-1) to (c1-5).

[0075] (In formulas (c1-1) to (c1-5), R １ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or —CH ２ -CR ３ R ３’ -OH(R ３ , R ３’ has the same definition as in formula (c-1), and m represents an integer of 1 to 8. ２ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３１ , L ３３ are each independently a single bond, —NR— (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —(CH ２ ) ｍ - (m is an integer from 1 to 6), or *1-(CH ２ ) ｍ-NR- (m is an integer of 1 to 6, R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, *1 represents a bond to the carbonyl carbon atom). ３２ represents a single bond, -NR- (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -(CH ２ ) ｍ - (m is an integer of 1 to 6), -CH=CH-, -CONH-, or -C(=O)-O-. n3 is an integer of 0 to 1. L ４１ , L ４２ , L ４３ , L ５ are each independently a single bond or -(CH ２ ) ｍ - (where m is an integer of 1 to 6). １ and R ２ may be the same or different.)

[0076] Preferred specific examples of the compound represented by any one of the above formulas (1c-1) to (1c-3) include compounds represented by any one of the following formulas (b1-1) to (b1-16).

[0077] A preferred example of the compound having the structure represented by the formula (c-1′) is a compound having the following formula (b １’ -1) to (b) １’ -2).

[0078] (Compound (C2)) From the viewpoint of suitably achieving the effects of the present invention, the molecular weight of compound (C2) is more preferably 2,000 or less, and preferably 150 or more. Furthermore, the molecular weight is still more preferably 200 to 1,800, and even more preferably 200 to 1,500. Examples of the a-valent organic group in formula (c-2) include an a-valent alicyclic hydrocarbon group; an a-valent aromatic hydrocarbon group; an a-valent heterocycle; an a-valent organic group (c2a) in which the carbon-carbon bond of an a-valent chain hydrocarbon group is substituted with at least one of an alicyclic hydrocarbon, an aromatic hydrocarbon, and a heterocycle; and an a-valent organic group (c2b) in which some or all of the hydrogen atoms of organic group (c2a) have been substituted with substituents. Specific examples of preferred a-valent alicyclic hydrocarbon groups include a-valent alicyclic hydrocarbon groups obtained by removing a hydrogen atoms from the alicyclic hydrocarbons having 3 to 30 carbon atoms exemplified for compound (C1) above. A specific preferred example of the a-valent aromatic hydrocarbon group includes an a-valent aromatic hydrocarbon group obtained by removing a hydrogen atoms from a hydrocarbon such as the aromatic hydrocarbon having 6 to 30 carbon atoms exemplified in compound (C1) above. A specific preferred example of the a-valent heterocycle includes an a-valent heterocycle obtained by removing a hydrogen atoms from the heterocycle exemplified in compound (C1) above. Specific examples of the a-valent chain hydrocarbon group in the a-valent organic group (c2a) include an organic group obtained by removing a hydrogen atoms from the chain hydrocarbon having 1 to 30 carbon atoms exemplified in compound (C1) above; a heteroatom-containing group containing a group having a heteroatom at least in a carbon-carbon bond of the organic group or at a terminal of the hydrocarbon group; and an organic group in which some or all of the hydrogen atoms in the chain hydrocarbon group and the heteroatom-containing group are substituted with substituents. Here, specific preferred examples of the group having a hetero atom in the heteroatom-containing group include groups having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a phosphorus atom, and a sulfur atom, such as -O-, -NR- (wherein R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CO-, -S-, and groups formed by combining these (-O-CO-, -NR-CO-, -NR-CO-NR-, etc.).Specific examples of the alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles in the a-valent organic group (c2a) include the aromatic hydrocarbons having 6 to 30 carbon atoms, the alicyclic hydrocarbons having 3 to 30 carbon atoms, and the heterocycles exemplified for the compound (C1) above. Specific preferred examples of the substituent in the organic group (c2b) include the substituents exemplified for the compound (C1) above. The a-valent organic group in the formula (c-2) above is preferably an a-valent organic group (a) having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms, and the organic group (a) may contain an oxygen atom, a sulfur atom, or a nitrogen atom within the group. From the viewpoint of suitably achieving the effects of the present invention, the a-valent organic group in the above formula (c-2) is more preferably an a-valent organic group having 6 to 40 carbon atoms in which an aromatic ring, a cyclohexane ring, or at least one cyclic group selected from the group consisting of these cyclic groups is linked by one or more linking groups (for example, a single bond, a chain hydrocarbon group, or a heteroatom-containing group). Examples of the aromatic ring include an aromatic hydrocarbon ring such as a benzene ring, and an aromatic heterocycle such as a pyridine ring.

[0079] Examples of the c2-valent organic group in Rc of the above formula (c-2') include a c2-valent chain hydrocarbon group; a c2-valent alicyclic hydrocarbon group; a c2-valent aromatic hydrocarbon group; a c2-valent heterocycle; a c2-valent organic group (c-2'-1) in which the carbon-carbon bond of a c2-valent chain hydrocarbon group is substituted with at least one of an alicyclic hydrocarbon, an aromatic hydrocarbon, and a heterocycle; a c2-valent hydrocarbon group (a chain hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an Examples of the c2-valent organic group include a c2-valent heteroatom-containing group (c-2'-2) containing a group having a heteroatom at least between carbon atoms or at the terminal of the c2-valent organic group (c-2'-1) (in addition to the heteroatom-containing groups described above, -C(=O)-N< is also included); and a c2-valent organic group (c-2'-3) in which some or all of the hydrogen atoms in (c-2'-1) to (c-2'-2) have been substituted with substituents. Specific examples of the c2-valent chain hydrocarbon group include organic groups in which c2 hydrogen atoms have been removed from the chain hydrocarbons having 1 to 30 carbon atoms exemplified for the compound (C1) above. Specific examples of the c2-valent alicyclic hydrocarbon group include c2-valent alicyclic hydrocarbon groups in which c2 hydrogen atoms have been removed from the alicyclic hydrocarbons having 3 to 30 carbon atoms exemplified for the compound (C1) above. A preferred example of the c2-valent aromatic hydrocarbon group is a c2-valent aromatic hydrocarbon group obtained by removing c2 hydrogen atoms from the aromatic hydrocarbon having 6 to 30 carbon atoms exemplified for the compound (C1) above. A preferred example of the c2-valent heterocycle is a c2-valent heterocycle obtained by removing c2 hydrogen atoms from the heterocycle exemplified for the compound (C1) above.

[0080] The compound represented by the formula (c-2) is more preferably a compound represented by the following formula (c ２Ｅ ) is a compound represented by the formula: (Formula (c ２Ｅ In the formula (c), Ra' represents a divalent organic group having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms, and the group Ra' may contain an oxygen atom, a sulfur atom, or a nitrogen atom. The bonding site between Ra' and N is an aliphatic carbon atom or an aromatic carbon atom. ２Ｅ Specific examples of the compound represented by the following formula (c ２Ｅ -1) to (c)２Ｅ -6)

[0081] Specific examples of the compound represented by the formula (c-2') include 1,3,5,6-tetrakis(glycidyloxy)-2,4-hexanediol, ２’ -1) to (c) ２’ -3)

[0082] The liquid crystal aligning agent of the present invention contains an organic solvent. Specific examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N,N-dimethylpropionamide, tetramethylurea, N,N-diethylformamide, 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 ...propionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N,N-diethylpropionamide, tetramethylurea, N, Examples of good solvents include propanamide, 3-butoxy-N,N-dimethylpropanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-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% by mass or more, and more preferably 30% by mass or more, when the total amount of all components in the liquid crystal aligning agent is 100% by mass.

[0083] Furthermore, the organic solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also referred to as a poor solvent) that improves the coatability and surface smoothness of the coating film when the liquid crystal aligning agent is applied. The content of the poor solvent is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, when the total mass of all components in the liquid crystal aligning agent is 100% by mass. The total content of the good solvent and the poor solvent is preferably 99.8% by mass or less, more preferably 98% by mass or less, when the total mass of all components in the liquid crystal aligning agent is 100% by 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. Specific examples of the poor solvent are listed below, but are not limited to these.

[0084] Diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether ethyl acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol diacetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, cyclohexyl acetate, 4-methyl-2-pentyl 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.

[0085] Of these, the poor solvent is preferably 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.

[0086] 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 monobutyl ether. 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-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether, N-ethyl-2-pyrrolidone, ethyl 3-ethoxypropionate and diethylene glycol monopropyl ether, 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 and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone, diethylene glycol monoethyl ether and butyl cellosolve acetate, N-methyl-2-pyrrolidone and diethylene glycol monomethyl ether and butyl cellosolve acetate, 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, 4-hydroxy-4-methyl-2-pentanone, and diisobutyl ketone, 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, N-ethyl-2-pyrrolidone, and 4-hydroxy-4-methyl -2-pentanone and dipropylene glycol dimethyl ether, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutylcarbinol, N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, diethylene glycol diethyl ether, and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and propylene glycol diacetate, N-ethyl-2-pyrrolidone, propylene glycol monobutyl ether, and diisobutyl ketone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and diisobutyl ketone, N-ethyl-2-pyrrolidone, N,N-dimethyl lactamide, and diisobutyl ketone, N-methyl-2-pyrrolidone, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate,Examples include γ-butyrolactone, ethylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone, ethylene glycol monobutyl ether acetate, and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone, 4-methyl-2-pentyl acetate, and ethylene glycol monobutyl ether, and N-methyl-2-pyrrolidone, cyclohexanone, and propylene glycol monomethyl ether.

[0087] The solids concentration of the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected taking into consideration viscosity, volatility, etc., but is preferably in the range of 1 to 10% by mass. From the viewpoint of forming a uniform, defect-free coating film, a concentration of 1% by mass or more is preferred, and from the viewpoint of the storage stability of the solution, a concentration of 10% by mass or less is preferred. A particularly preferred solids concentration is 2 to 8% by mass. The solids concentration range may be appropriately selected depending on the method used to apply the liquid crystal aligning agent to the substrate. For example, when spin coating is performed, a solids concentration of 1.5 to 4.5% by mass is particularly preferred. When using a printing method, a solids concentration of 3 to 9% by mass is particularly preferred, thereby resulting in a solution viscosity of 12 to 50 mPa·s. When using an inkjet method, a solids concentration of 1 to 5% by mass is particularly preferred, thereby resulting in a solution viscosity of 3 to 15 mPa·s. The temperature when preparing the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C. The concentration of the polymer component in the liquid crystal aligning agent can be appropriately changed depending on the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, the concentration of the polymer component in the liquid crystal aligning agent (total concentration of polymers) is preferably 1% by mass or more, and from the viewpoint of solution storage stability, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass. From the viewpoint of suitably obtaining the effects of the present disclosure, the content of the polymer component (P) in the liquid crystal aligning agent (total amount of polymers constituting the polymer component (P)) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 50 parts by mass or more, relative to a total of 100 parts by mass of the polymer components contained in the liquid crystal aligning agent. When the liquid crystal aligning agent contains other polymers described below, the content of the polymer component (P) is preferably 99.9 parts by mass or less, more preferably 99 parts by mass or less, relative to a total of 100 parts by mass of the polymers contained in the liquid crystal aligning agent.

[0088] The liquid crystal aligning agent of the present invention may contain other components as necessary. Examples of such components include other polymers than the polymer (p) and the polyimide precursors (A) and (B); at least one compound selected from the group consisting of crosslinkable compounds having at least one substituent selected from an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and a crosslinkable compound having a polymerizable unsaturated group; crosslinkable compounds having an epoxy group other than the compounds (C1) and (C2); functional silane compounds; metal chelate compounds; curing accelerators; surfactants; antioxidants; sensitizers; preservatives; compounds for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film; and compounds for promoting imidization.

[0089] Specific examples of other polymers include polymers selected from the group consisting of polysiloxane, polyester, polyamide, polyurea, polyurethane, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene derivatives, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate.

[0090] Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, and 3000 (manufactured by Cray Valley) and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.). Specific examples of poly(isobutylene-maleic anhydride) copolymers include ISOBAN-600 (manufactured by Kuraray Co., Ltd.). Specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland). One type of other polymer may be used alone, or two or more types may be used in combination. The content of the other polymer is preferably 90 parts by mass or less, and more preferably 80 parts by mass or less, relative to a total of 100 parts by mass of the polymers contained in the liquid crystal aligning agent. Furthermore, the content of the other polymer is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, relative to a total of 100 parts by mass of the polymers contained in the liquid crystal aligning agent.

[0091] Preferable specific examples of the crosslinkable compound include compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO2011 / 132751; Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation); and Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.). compounds having a blocked isocyanate group such as 2,2'-bis(2-oxazoline), 2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(5-methyl-2-oxazoline), 1,2,4-tris(2-oxazolinyl)-benzene, and EPOCROS (manufactured by Nippon Shokubai Co., Ltd.); compounds having a cyclocarbonate group such as those described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; Compounds having a hydroxy group or an alkoxy group, such as 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane; glycerin mono(meth)acrylate, glycerin di(meth)acrylate ( 1,2-, 1,3-dimer mixture), glycerin tris(meth)acrylate, glycerin 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate;Ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, bisphenol A type epoxy resins such as Epicoat 828 (manufactured by Mitsubishi Chemical Corporation), Epicoat 807 (manufactured by Mitsubishi Chemical Corporation), etc. Examples of suitable crosslinkable compounds include bisphenol F epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), hydrogenated bisphenol A epoxy resins such as YX-8000 (manufactured by Mitsubishi Chemical Corporation), biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenol novolac epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), and alicyclic epoxy resins such as CELLOXIDE 2021P (manufactured by Daicel Corporation). The content of the crosslinkable compound 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 aligning agent.

[0092] Examples of the compound for adjusting the dielectric constant or electrical resistance include monoamines having a nitrogen atom-containing aromatic heterocycle such as 3-picolylamine. The content of the monoamine having a nitrogen atom-containing aromatic heterocycle 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 aligning agent.

[0093] Specific preferred examples of the functional silane compound 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, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris[3-(trimethoxysilyl)propyl]isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc. The content of the functional silane compound 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.

[0094] The compound for promoting the imidization is preferably a compound having a basic site (e.g., a primary amino group, an aliphatic heterocycle (e.g., a pyrrolidine skeleton), an aromatic heterocycle (e.g., an imidazole ring, an indole ring), or a guanidino group) (excluding the crosslinkable compound and the adhesion aid), or a compound that generates the basic site upon baking. A more preferred example is a compound that generates the basic site upon baking, and preferred specific examples include amino acids in which some or all of the basic sites of the amino acid are protected. Examples of protecting groups for the basic sites of the amino acids include carbamate protecting groups such as a Boc group. Specific examples of the amino acids include glycine, alanine, cysteine, methionine, asparagine, glutamine, valine, leucine, phenylalanine, tyrosine, tryptophan, proline, hydroxyproline, arginine, histidine, lysine, and ornithine. More preferred specific examples of the compound for promoting imidization include N-α-(9-fluorenylmethoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine or N-α-(tert-butoxycarbonyl)-N-τ-(tert-butoxycarbonyl)-L-histidine. The content of the compound for promoting imidization contained in the liquid crystal aligning agent of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0095] (Liquid Crystal Alignment Film and Liquid Crystal Display Element) The liquid crystal display element according to the present invention comprises a liquid crystal alignment film formed using the liquid crystal aligning agent described above. The liquid crystal alignment film of the present invention can be produced, for example, by a method including the following steps (1) and (2) or a method including the following steps (1) to (3). The operation mode of the liquid crystal display element is not particularly limited, and it can be applied to various operation modes, such as the TN mode, STN mode, vertical alignment mode (including the VA-MVA mode, the VA-PVA mode, etc.), in-plane switching mode (IPS mode, FFS mode), and optically compensated bend mode (OCB mode).

[0096] The liquid crystal display element of the present invention can be manufactured by, for example, a method including the following steps (1) to (4), a method including steps (1) to (2) and (4), a method including steps (1) to (3), (4-2) and (4-4), or a method including steps (1) to (3), (4-3) and (4-4). One embodiment of the liquid crystal display element of the present invention is a liquid crystal display element having a liquid crystal alignment film formed by a method for manufacturing a liquid crystal alignment film including the following steps (1) to (2) or steps (1) to (3).

[0097] <Step (1): Applying a Liquid Crystal Alignment Agent to a Substrate> Step (1) is a step of applying a liquid crystal alignment agent to a substrate. A specific example of step (1) is as follows: The liquid crystal alignment agent 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 material is not particularly limited as long as it is highly transparent; glass, silicon nitride, and plastics such as acrylic and polycarbonate can also be used. In addition, in a reflective liquid crystal display element, 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 an IPS or FFS liquid crystal display element, 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. An IPS substrate, which is a comb electrode substrate used in an IPS-mode liquid crystal display element, has, for example, a base material, a plurality of linear electrodes formed on the base material and arranged in a comb-teeth pattern, and a liquid crystal alignment film formed on the base material so as to cover the linear electrodes. Meanwhile, an FFS substrate, which is a comb electrode substrate used in an FFS-mode liquid crystal display element, has, for example, a base material, a surface electrode formed on the base material, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-teeth pattern, and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

[0098] 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.

[0099] <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. Specific examples of step (2) are as follows. After applying the liquid crystal alignment agent to the substrate in step (1), the solvent can be evaporated or a polyimide precursor, such as polyamic acid, can be thermally imidized using a heating means such as a hot plate, a hot air circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal alignment agent can be performed at any temperature and for any time, and may be performed multiple times. The temperature at which the liquid crystal alignment agent is baked can be, for example, 40 to 180°C. From the perspective of shortening the process, it may be performed at 40 to 150°C. The baking time is not particularly limited, but may be 1 to 10 minutes or 1 to 5 minutes. When thermal imidization of a polyimide precursor, such as polyamic acid, is carried out, a baking step may be added after the above step, for example, at 150 to 300°C or 150 to 250°C. The baking time is not particularly limited, but examples include baking times of 5 to 40 minutes or 5 to 30 minutes. If the film-like material after baking is too thin, the reliability of the liquid crystal display element may decrease, so the film thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0100] <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 mode liquid crystal display elements 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 mode liquid crystal display elements such as VA mode or PSA mode, the formed coating film can be used as a liquid crystal alignment film as is, or the coating film may be subjected to an alignment ability imparting treatment. Alignment treatment methods for liquid crystal alignment films include rubbing alignment treatment and photoalignment treatment. Photoalignment treatment methods include irradiating the surface of the film-like material with radiation, preferably polarized in a certain direction, and then preferably performing a heat treatment 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 200 to 400 nm is more preferred.

[0101] 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. Furthermore, 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 thus prepared can stably align liquid crystal molecules in a specific direction. Examples of light sources that can be used for the irradiation light include low-pressure mercury lamps, high-pressure mercury lamps, deep UV lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, mercury-xenon lamps, excimer lasers (e.g., KrF excimer lasers), fluorescent lamps, LED lamps, halogen lamps (e.g., sodium lamps), and microwave-excited electrodeless lamps. Furthermore, when polarized light is used as the irradiation light, a higher extinction ratio of polarized light can impart higher anisotropy. Therefore, in the case of ultraviolet light, for example, the extinction ratio of polarized ultraviolet light is more preferably 10:1 or more, and even more preferably 20:1 or more.

[0102] Furthermore, the coating film irradiated with polarized radiation or the coating film subjected to rubbing alignment treatment by the above method may be subjected to a contact treatment using water or a solvent. Furthermore, the film subjected to the above alignment treatment may be subjected to a heat treatment without being subjected to a contact treatment. Furthermore, the film subjected to the above contact treatment may be further subjected to a heat treatment.

[0103] 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. 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. The solvent may be used alone or in combination of two or more.

[0104] The temperature for the heat treatment of the coating film irradiated with radiation or the film that has been contact-treated is preferably 50 to 300° C., more preferably 120 to 300° C., even more preferably 150 to 300° C., and most preferably 150 to 250° C. The heat treatment time is preferably 1 to 30 minutes.

[0105] <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.

[0106] 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 desirable to further heat the substrate to a temperature at which the liquid crystal composition 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 alignment treatment, the two substrates are positioned opposite each other so that the rubbing directions of the coating films are at a predetermined angle to each other, for example, perpendicular or antiparallel. For example, an epoxy resin containing a curing agent and aluminum oxide spheres as spacers can be used as the sealant. The liquid crystal composition is not particularly limited, and may be a composition containing at least one liquid crystal compound (liquid crystal molecule), such as a liquid crystal composition exhibiting a nematic phase (hereinafter also referred to as nematic liquid crystal), a liquid crystal exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase. Among these, nematic liquid crystal is preferred. Furthermore, various liquid crystal compositions having positive or negative dielectric anisotropy may be used. Hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative liquid crystal. The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring, or may contain a compound having two or more rigid moieties (mesogenic skeletons) that exhibit liquid crystallinity in the molecule (e.g., a bimesogenic compound in which two rigid biphenyl structures or terphenyl structures are linked by an alkyl group). Furthermore, the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal alignment properties.Such additives include photopolymerizable monomers such as compounds having a polymerizable group (e.g., a (meth)acryloyl group); optically active compounds (e.g., S-811 manufactured by Merck Co., Ltd.); antioxidants; ultraviolet absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors. Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, and MLC-7081 manufactured by Merck Co., Ltd. Negative liquid crystals include MLC-6608, MLC-6609, MLC-6610, MLC-7026, and MLC-7026-100 manufactured by Merck Co., Ltd. Furthermore, an example of a liquid crystal containing a compound having a polymerizable group is MLC-3023 manufactured by Merck Co., Ltd.

[0107] The liquid crystal aligning agent of the present invention is also preferably used in a liquid crystal display element (PSA-type liquid crystal display element) manufactured by a process of: having a liquid crystal layer between a pair of substrates equipped with electrodes, disposing a liquid crystal composition containing a polymerizable compound that polymerizes by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between the electrodes. The liquid crystal aligning agent of the present invention is also preferably used in a liquid crystal display element (SC-PVA-type liquid crystal display element) manufactured by a process of having a liquid crystal layer between a pair of substrates equipped with electrodes, disposing a liquid crystal alignment film between the pair of substrates that contains a polymerizable group that polymerizes by at least one of active energy rays and heat, and applying a voltage between the electrodes.

[0108] <Step (4-2): In the case of a PSA-type liquid crystal display element> This step is carried out in the same manner as in the above step (4), except that a liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds having one or more polymerizable unsaturated groups, such as an acrylate group or a methacrylate group, in the molecule.

[0109] <Step (4-3): In the Case of an SC-PVA-Type Liquid Crystal Display Element> A method for producing a liquid crystal display element may be employed, in which a process similar to that described in (4) above is followed by a step of irradiating with ultraviolet light, as described below. This method, similar to the production of a PSA-type liquid crystal display element, allows for the production of a liquid crystal display element with excellent response speed with a low light exposure dose. The compound having a polymerizable group may be a compound having one or more of the above-described polymerizable unsaturated groups in its molecule, and its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. Furthermore, the polymerizable group may be contained in the polymer used in the liquid crystal aligning agent. Examples of such polymers include polymers obtained by reacting a diamine component containing a diamine having the above-described photopolymerizable group at its terminal.

[0110] <Step (4-4): Step of Irradiating Ultraviolet Light> The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in step (4-2) or (4-3) above. The voltage applied here can be, for example, a direct current or alternating current of 5 to 50 V. The light to be irradiated can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiation light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. The light irradiation dose is preferably 1,000 to 200,000 J / m ２ and more preferably 1,000 to 100,000 J / m ２ is.

[0111] 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.

[0112] 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 for compounds and solvents are as follows. (Organic solvents) NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone BCS: butyl cellosolve (Diamines) DA-1 to DA-13: Compounds represented by the following structural formulas (DA-1) to (DA-13), respectively (Tetracarboxylic acid dianhydrides) CA-1 to CA-4: Compounds represented by the following structural formulas (CA-1) to (CA-4), respectively (Additives) AD-1: 3-glycidoxypropyltriethoxysilane AD-3: Compound represented by the following structural formula (AD-3) AD-6 to AD-7: Compounds represented by the following structural formulas (AD-6) to (AD-7), respectively (Crosslinking agents) AD-2, AD-4, AD-8 to AD-11: Compounds represented by the following structural formulas (AD-2), (AD-4), (AD-8), (AD-9), (AD-10), and (AD-11), respectively. AD-5: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane. Of the above crosslinking agents, AD-2, AD-4, and AD-11 are included in the range of compounds corresponding to compound (C1) of the present application. Furthermore, AD-5 and AD-8 to AD-10 are included in the range of compounds corresponding to compound (C2) of the present application.

[0113] [Synthesis of Polymers] (Synthesis Example 1) 0.22 g (2.0 mmol) of DA-1, 0.73 g (3.0 mmol) of DA-2, 0.96 g (3.0 mmol) of DA-7, and 0.80 g (2.0 mmol) of DA-8 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 31.1 g of NMP was added. The mixture was stirred while supplying nitrogen to dissolve the diamine solution. While stirring under water cooling, 2.10 g (9.4 mmol) of CA-4 was added, and then 4.1 g of NMP was added, and the mixture was stirred at 40°C under a nitrogen atmosphere for 3 hours to obtain a polyamic acid solution of Polymer-1.

[0114] Synthesis Example 2: 0.16 g (1.5 mmol) of DA-1, 0.73 g (3.0 mmol) of DA-2, 0.54 g (2.0 mmol) of DA-6, 0.68 g (2.0 mmol) of DA-10, and 0.18 g (1.5 mmol) of DA-9 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 27.8 g of NMP was added. The mixture was dissolved by stirring while supplying nitrogen. While stirring this diamine solution under water cooling, 2.10 g (9.4 mmol) of CA-4 was added, and then 5.5 g of NMP was added, and the mixture was stirred at 40° C. under a nitrogen atmosphere for 3 hours to obtain a polyamic acid solution of polymer-2.

[0115] Synthesis Example 3: 0.86 g (8.0 mmol) of DA-1 and 0.22 g (2.0 mmol) of DA-3 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 10.9 g of NMP was added. The mixture was stirred and dissolved while supplying nitrogen. While stirring this diamine solution under water cooling, 1.37 g (7.0 mmol) of CA-3 was added, and then 7.1 g of NMP was added, and the mixture was stirred for 2 hours at 25°C under a nitrogen atmosphere. Thereafter, 0.63 g (2.5 mmol) of CA-2 was added, and then 4.6 g of NMP was added, and the mixture was stirred for 12 hours at 50°C under a nitrogen atmosphere to obtain a polyamic acid solution of Polymer-3.

[0116] Synthesis Example 4: 1.59 g (8.0 mmol) of DA-4 and 0.30 g (2.0 mmol) of DA-5 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, 17.1 g of NMP was added, and the mixture was dissolved by stirring while supplying nitrogen. While stirring this diamine solution under water cooling, 2.82 g (9.6 mmol) of CA-1 was added, and then 17.5 g of NMP was added, and the mixture was stirred at 70°C under a nitrogen atmosphere for 2 hours to obtain a polyamic acid solution of Polymer-4.

[0117] Synthesis Example 5: 1.59 g (8.0 mmol) of DA-4 and 0.60 g (2.0 mmol) of DA-11 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 25.2 g of NMP was added. The mixture was stirred and dissolved while supplying nitrogen. While stirring this diamine solution under water cooling, 2.82 g (9.6 mmol) of CA-1 was added, and then 11.6 g of NMP was added, and the mixture was stirred at 70°C for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution of Polymer-5.

[0118] Synthesis Example 6: 1.20 g (6.0 mmol) of DA-4, 0.60 g (2.0 mmol) of DA-11, and 0.84 g (2.0 mmol) of DA-12 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 30.3 g of NMP was added. The mixture was stirred and dissolved while supplying nitrogen. While stirring this diamine solution under water cooling, 2.82 g (9.6 mmol) of CA-1 was added, and then 9.7 g of NMP was added. The mixture was stirred at 70°C for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution of Polymer-6.

[0119] Synthesis Example 7: 0.16 g (1.5 mmol) of DA-1, 0.73 g (3.0 mmol) of DA-2, 0.54 g (2.0 mmol) of DA-6, 0.80 g (2.0 mmol) of DA-8, and 0.18 g (1.5 mmol) of DA-9 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 27.8 g of NMP was added. The mixture was stirred and dissolved under nitrogen flow. While stirring this diamine solution under water cooling, 2.10 g (9.4 mmol) of CA-4 was added, followed by 5.5 g of NMP. The mixture was stirred at 40°C for 3 hours under a nitrogen atmosphere to obtain a polyamic acid solution, Polymer-7. The types and amounts of the tetracarboxylic acid component and diamine component used in Synthesis Examples 1 to 7 are shown in Table 1. In Table 1, the numerical values ​​for the tetracarboxylic acid component and diamine component represent the proportion (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.

[0120] Synthesis Example 8: 1.59 g (8.0 mmol) of DA-4 and 0.22 g (2.0 mmol) of DA-1 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, 13.3 g of NMP was added, and the mixture was stirred and dissolved while supplying nitrogen. While stirring this diamine solution under water cooling, 1.85 g (9.4 mmol) of CA-3 was added, and then 13.6 g of NMP was added, and the mixture was stirred at 25°C for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution of Polymer-8.

[0121] Synthesis Example 9 1.79 g (6.0 mmol) of DA-11 and 0.60 g (4.0 mmol) of DA-13 were weighed into a 100 mL recovery flask equipped with a stirrer and a nitrogen inlet tube, and 17.5 g of NMP was added. The mixture was stirred and dissolved while supplying nitrogen. While stirring this diamine solution under water cooling, 1.85 g (9.4 mmol) of CA-3 was added, and then 13.6 g of NMP was added, and the mixture was stirred at 25° C. for 2 hours under a nitrogen atmosphere to obtain a polyamic acid solution of Polymer-9.

[0122]

[0123] [Preparation of liquid crystal aligning agent] (Liquid crystal aligning agent A-1) In a 100 mL Erlenmeyer flask containing a stirrer, a solution (16.7 g) of the polymer (polymer-1) obtained in Synthesis Example 1 and a solution (25.0 g) of the polymer (polymer-3) obtained in Synthesis Example 3 were weighed out, and NMP (22.7 g), BCS (30.0 g) and a 10 mass% NMP solution (1.7 g) of AD-1 and a 10 mass% NMP solution (4.0 g) of AD-2 were added and stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (A-1). (Liquid crystal aligning agents A-2 to A-13) The same operation as in Example 1 was performed except that the types and amounts of the polymer solution, solvent, and additives used were changed as shown in Table 2 below. Liquid crystal aligning agents (A-2) to (A-13) were obtained. Among the additives in Table 2, AD-1, AD-2, AD-4, AD-5, AD-8, AD-9, AD-10, and AD-11 were each added as a 10% by mass NMP solution.

[0124]

[0125] [Fabrication of Liquid Crystal Display Element] (Configuration of FFS-Driven Liquid Crystal Cell) A liquid crystal cell having the configuration of a fringe field switching (FFS) mode liquid crystal display element was fabricated. First, a first glass substrate with electrodes was prepared. The substrate was a 35 mm x 40 mm glass substrate with a thickness of 0.7 mm. A solid-patterned ITO electrode constituting a counter electrode was formed on the substrate as a first layer. A SiN (silicon nitride) film formed by CVD was formed on the first counter electrode as a second layer. The second SiN film had a thickness of 500 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, forming two pixels, a first pixel and a second pixel. Each pixel measured 10 mm long and approximately 5 mm wide. The first-layer counter electrode and the third-layer pixel electrode were electrically insulated by the action of the second-layer SiN film. The third-layer pixel electrode had a comb-like shape in which multiple 3-μm-wide electrode elements, each bent at an interior angle of 160° at the center, were arranged parallel to each other at 6-μm intervals. Each pixel had a first region and a second region separated by a line connecting the bent portions of the multiple electrode elements. The liquid crystal alignment film formed on the first glass substrate was oriented so that the direction dividing the interior angle of the pixel bend was perpendicular to the alignment direction of the liquid crystal. The liquid crystal alignment film formed on the second glass substrate (described later) was oriented so that the alignment direction of the liquid crystal on the first substrate was aligned with the alignment direction of the liquid crystal on the second substrate when the liquid crystal cell was fabricated. Next, a liquid crystal alignment agent filtered through a filter with a pore size of 1.0 μm was spin-coated onto the above-mentioned electrode-attached substrate (first glass substrate) and a second glass substrate having a 4 μm-high columnar spacer with an ITO film formed on the back surface, and dried for 2 minutes on a hot plate at 80° C. Thereafter, the substrate was baked for 30 minutes in an infrared heating furnace at 230° C. to obtain a substrate with a liquid crystal alignment film having a film thickness of 80 nm.

[0126] (Photo-Alignment Treatment) Linearly polarized ultraviolet light with a wavelength of 254 nm and an extinction ratio of 10:1 or greater was irradiated through a polarizing plate. A heating step was then performed in an infrared heating furnace at 230°C for 30 minutes to obtain a substrate with a liquid crystal alignment film. Two types of substrates with the above liquid crystal alignment film were prepared, and a sealant (Mitsui Chemicals XN-1500T) was printed around the periphery, leaving only the liquid crystal injection port. The substrates were then bonded together so that the liquid crystal alignment film surfaces faced each other and the alignment direction was 0°. The sealant was then cured to produce an empty cell with a cell gap of 4 μm. Liquid crystal MLC-7026-100 (Merck) was vacuum-injected into this empty cell at room temperature, and the injection port was sealed to produce an FFS-driven liquid crystal cell. The resulting FFS-driven liquid crystal cell was heated at 120°C for 1 hour and then left overnight at 23°C before being used for the following evaluations.

[0127] [Evaluation of Image Retention Characteristics Under Long-Term AC Operation] An AC voltage of ±5.8 V at a frequency of 60 Hz was applied to the FFS-driven liquid crystal cell prepared above for 120 hours at a constant temperature of 60°C. The pixel electrode and counter electrode of the liquid crystal cell were then shorted and left at room temperature for one day. For the liquid crystal cell subjected to the above treatment, the deviation between the alignment direction of the liquid crystal molecules in the first region of the pixel and the alignment direction of the liquid crystal molecules in the second region of the pixel in the no-voltage state was calculated as the angle Δθ. Specifically, the liquid crystal cell was placed between two polarizing plates arranged so that their polarization axes were perpendicular to each other. A backlight was turned on, and the alignment angle of the liquid crystal cell was adjusted so that the transmitted light intensity of the first region of the pixel was minimized. The rotation angle (Δθ) required to rotate the liquid crystal cell so that the transmitted light intensity of the second region of the pixel was minimized was then calculated. It can be said that the smaller the rotation angle, the better the image retention characteristics under long-term AC operation. Specifically, a rotation angle of 0.10 degrees or less was evaluated as "A", a rotation angle of more than 0.10 degrees and less than 0.15 degrees was evaluated as "O", and a rotation angle of more than 0.15 degrees was evaluated as "X". The results are shown in Table 3.

[0128] [Adhesion Evaluation] (Sample Preparation) A sample for adhesion evaluation was prepared as follows. A liquid crystal alignment agent prepared by spin coating was applied to a 30 mm x 40 mm ITO substrate. After drying for 2 minutes on a hot plate at 80°C, it was baked for 30 minutes in an infrared heating furnace at 230°C to form a coating film with a thickness of 100 nm. 254 nm ultraviolet light was irradiated on the coating film surface through a polarizer at 500 mJ / cm. ２ The substrate was irradiated with light to obtain a substrate with a liquid crystal alignment film. Two substrates were prepared in this manner, and 4 μm bead spacers were applied to the liquid crystal alignment film surface of one substrate, after which a sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was dripped onto it. Next, the liquid crystal alignment film surface of the other substrate was placed inside, and the substrates were bonded together so that the overlap width was 1 cm. At this time, the amount of sealant dripped was adjusted so that the diameter of the sealant after bonding was 3 mm. The two bonded substrates were fixed with clips and then thermally cured at 150°C for 1 hour to prepare a sample for adhesion evaluation.

[0129] (Measurement of Adhesion) The sample substrate was then fixed at the edges of the upper and lower substrates using a Shimadzu Corporation tabletop precision universal testing machine (EZ-SX 100N), and the substrate was pressed from above the center to measure the pressure (N) applied during peeling. The obtained measured value (N) was divided by the diameter (mm) of the applied sealant to evaluate the adhesion. Values ​​higher than 6.5 N / mm were evaluated as good and marked with "◯", while values ​​below 6.5 N / mm were evaluated as "×". The results are shown in Table 3.

[0130]

[0131] By using a liquid crystal display element having the configuration of the present invention, a liquid crystal display element having a liquid crystal alignment film with excellent adhesion and capable of suppressing AC afterimages to a high level can be obtained. These elements are useful not only for liquid crystal displays for display purposes, but also for light control windows and optical shutters that control the transmission and blocking of light.

Claims

1. A liquid crystal aligning agent containing a polymer component (P) containing one or more types of polymers, a compound (C1), and a compound (C2), wherein the polymer component (P) contains at least one polymer (p) selected from the group consisting of polyimide precursors and polyimides that are imidized products of the polyimide precursors. Compound (C1): A compound having two or more structures represented by any one of the following formulas (c-1) to (c-1'). Compound (C2): A compound represented by any one of the following formulas (c-2) to (c-2'). (In formula (c-1), R ２ and R ２’ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group "*3-CH ２ -O-R １１ ” (R １１ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ and R ２’ represents a bond to the carbon atom to which it is bonded. ３ and R ３’ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. *1 and *2 represent a bond. n1 represents an integer of 0 or 1. In formula (c-1'), R ４２ and R ４２ ' are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a group "*43-CH ２ -O-R ４１ ” (R ４１ represents a monovalent group having a tetrahydropyran ring structure or an alkyl group having 1 to 3 carbon atoms. ４２ and R ４２’ represents a bond to the carbon atom to which it is bonded. ４３ and R ４３ Each of the ' independently represents a hydrogen atom, a monovalent group having a tetrahydropyran ring structure, or an alkyl group having 1 to 3 carbon atoms. n41 represents an integer of 0 or 1. Dx represents a monovalent group having a tetrahydropyran ring structure. *1 and *2 are synonymous with *1 and *2 in formula (c-1). In formula (c-2), a represents an integer of 2 to 4, Ra represents an a-valent organic group, and the bonding sites to the a N atoms are aliphatic carbon atoms or aromatic carbon atoms. In formula (c-2'), c1 represents an integer of 1 to 6, Rc represents a c2-valent organic group, and the bonding site to the oxygen atom is an aliphatic carbon atom or aromatic carbon atom. c2 is an integer of 3 to 4.

2. The liquid crystal aligning agent according to claim 1, wherein the compound (C1) is a compound represented by any one of the following formulas (1c-1) to (1c-4): (In formulas (1c-1) to (1c-3), W represents an n-valent organic group. n represents an integer of 2 to 6. R １ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ represents —OH. ４ and R ５ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ represents —OH, and a plurality of R ４ and R ５ At least two of the following are -(CR ２ R ２’ ) ｎ１ -CR ３ R ３’ n1, R represents —OH. ２ , R ２’ , R ３ , R ３’ has the same definition as in formula (c-1). ４ represents an n-valent organic group (n ４０ represents an integer of 2 to 6.) R ４１ , R ４２ , R ４２’ , R ４３ , R ４３’ , Dx and n41 are defined as in formula (c-1').

3. The compound represented by the formula (c-2) is a compound represented by the following formula (c ２Ｅ The liquid crystal aligning agent according to claim 1, wherein the compound is a compound represented by the formula: (Formula (c ２Ｅ In the formula, Ra' represents a divalent organic group having an aromatic ring or a cyclohexane ring and having 6 to 40 carbon atoms, and the group Ra' may contain an oxygen atom, a sulfur atom, or a nitrogen atom. The bonding site between Ra' and N is an aliphatic carbon atom or an aromatic carbon atom.

4. The liquid crystal aligning agent according to claim 1, wherein the polymer (p) has one or more structural units, and has at least one structural unit selected from the group consisting of a structural unit (p0) represented by the following formula (P0) and an imidized structural unit of the structural unit (p0): (In formula (P0), X represents a tetravalent organic group, Y represents a divalent organic group, and multiple R's and Z's each independently represent a hydrogen atom or a monovalent organic group.) 5. The liquid crystal aligning agent according to claim 4, wherein the divalent organic group of Y in formula (P0) is a divalent organic group represented by any one of the following formulas (3) to (4): (In formulas (3) and (4), R ３ , R ４ , and R ４’ A each independently represents a halogen atom, a hydroxy group, an optionally protected amino group, a thiol group, a nitro group, a phosphate group, or a monovalent organic group having 1 to 20 carbon atoms. ４ represents an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 20 carbon atoms, provided that 1,4-phenylene group, 1 to 4 of the hydrogen atoms on the phenylene group are R ４ , and R ４’ a3, a4, and a4' are each independently an integer of 0 to 4. a is an integer of 1 to 4. b and c are each independently an integer of 1 or 2. R ３ , R ４ , R ４’ If there are multiple R ３ , R ４ , and R ４’ The structures of may be the same or different. When a plurality of a3, a4, and a4' are present, they may be the same or different. * represents a bond.

6. The liquid crystal aligning agent according to claim 1, wherein the polymer (p) is a polymer containing a structural unit having a divalent organic group selected from the group consisting of a divalent organic group having a urea bond, a divalent organic group having an amide bond, a divalent organic group having at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group, and a tertiary amino group, and a divalent organic group having a carboxy group.

7. The liquid crystal aligning agent according to claim 1, wherein the polymer constituting the polymer component (P) does not have an acid-dissociable group.

8. A liquid crystal aligning agent containing a polymer component (P) containing two or more polymers, wherein the polymer component (P) satisfies at least one of the following conditions (i) to (iii): (i) a polymer component (P1) containing two or more polymers selected from the group consisting of a polyimide precursor (A) having one or more structural units and having a structural unit (a1) represented by the following formula (A1) and a polyimide which is an imidized product of the polyimide precursor; (ii) a polymer component (P2) containing two or more polyimide precursors (B) which are polymers different from the polyimide precursor (A), having one or more structural units and having a structural unit (b1) represented by the following formula (B1); and (iii) a polymer component (P3) containing the polyimide precursor (B) and at least one polymer selected from the group consisting of the polyimide precursor (A) and a polyimide which is an imidized product of the polyimide precursor. (In formula (A1), X ａ１ represents a tetravalent organic group selected from the group consisting of the following formulae (Xa1-1) to (Xa1-8), and Y ａ１ represents a divalent organic group. A plurality of R's and Z's each independently represent a hydrogen atom or a monovalent organic group. (In formulas (Xa1-1) to (Xa1-8), R １ From R １５ 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 containing a fluorine atom, or a phenyl group, and may be the same or different. * represents a bond.) (In formula (B1), X ｂ１ represents a tetravalent organic group having an aromatic group having 6 to 30 carbon atoms; X ｂ１ At least one of the carbonyl carbons bonded to X ｂ１ It bonds to the aromatic group of Y. ｂ１ represents a divalent organic group. A plurality of R's and Z's each independently represent a hydrogen atom or a monovalent organic group.

9. A liquid crystal alignment film obtained from the liquid crystal aligning agent according to any one of claims 1 to 8.

10. A method for producing a liquid crystal alignment film, comprising the following steps (1) to (3): Step (1): applying the liquid crystal alignment agent according to any one of claims 1 to 8 onto a substrate; Step (2): baking the applied liquid crystal alignment agent; Step (3): performing an alignment treatment on the film obtained in Step (2).

11. The method for producing a liquid crystal alignment film according to claim 10, wherein the alignment treatment is a photo-alignment treatment.

12. The method for producing a liquid crystal alignment film according to claim 11, further comprising the following baking step after the step (3): Baking step: a step of baking at 150°C to 300°C.

13. A liquid crystal alignment film formed by the method for producing a liquid crystal alignment film according to claim 10.

14. A liquid crystal display device comprising the liquid crystal alignment film according to claim 9.

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

16. A method for manufacturing a liquid crystal display element, comprising forming the liquid crystal alignment film according to claim 9.

17. A method for manufacturing a liquid crystal display element, comprising forming the liquid crystal alignment film according to claim 13.

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