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

Abstract

Provided are: a liquid crystal alignment agent which can obtain a liquid crystal alignment film in which migration of silver is suppressed and which has a high voltage holding ratio even after being exposed for a long period of time under high temperature; the liquid crystal alignment film obtained from the liquid crystal alignment agent; and a liquid crystal display element using the same. Provided is the liquid crystal alignment agent containing component (A) below and the compound (B) represented by formula (1) below. Component (A) is a polymer (A) selected from the group consisting of: a polyimide precursor obtained by a polymerization reaction brought about between a diamine component and a tetracarboxylic acid derivative component including at least one compound selected from the group consisting a tetracarboxylic dianhydride and a derivative thereof; and a polyimide which is an imide compound of said polyimide precursor, the content of carboxy groups bonded to aromatic rings in the polymer being 5 parts by mass with respect to 100 parts by mass of the polymer. [Formula 1] (In the formula A1 represents a hydrogen atom or a univalent group having a trialkoxysilyl group, and A2 each independently represent a C1-4 alkyl group or alkoxy group, or a hydrogen atom.)

Description

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

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

[0002] Various driving methods have been developed for liquid crystal display elements, which differ in electrode structure, physical properties of the liquid crystal molecules used, manufacturing process, etc. Known liquid crystal display elements include, for example, TN (twisted nematic) type, STN (super-twisted nematic) type, VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field switching) type, PSA (polymer-sustained alignment) type, etc. These liquid crystal display elements are equipped with a liquid crystal alignment film to align the liquid crystal molecules. As the material for the liquid crystal alignment film, a coating made of a polymer such as polyamic acid, polyimide, or polysiloxane is generally used because of its excellent properties such as heat resistance, mechanical strength, and affinity with liquid crystals.

[0003] As the definition of liquid crystal display elements increases, there are demands for suppressing a decrease in contrast of liquid crystal display elements and reducing the phenomenon of afterimages. In addition to exhibiting excellent liquid crystal alignment properties and a stable pretilt angle, liquid crystal alignment films are increasingly required to have properties such as a high voltage holding ratio, suppression of afterimages caused by AC driving, small residual charge when a DC voltage is applied, and / or rapid relaxation of residual charge accumulated by a DC voltage. Various proposals have been made for polyimide-based liquid crystal alignment films to meet the above-mentioned demands (see Patent Documents 1 to 5).

[0004] On the other hand, it is known that the use of specific metal materials for the electrodes and wiring of liquid crystal display elements can cause various problems. For example, when using electrodes and wiring containing copper or aluminum, a document is known that proposes using a liquid crystal alignment film with a side chain containing a benzotriazole group to solve these problems (see Patent Document 6). However, since it is necessary to introduce a characteristic structure into the side chain of the polymer, the design freedom of the liquid crystal alignment film is limited, and an alternative solution has been sought.

[0005] In addition, there is also a known document that addresses a similar problem by adding a component containing a benzotriazole group to the liquid crystal (see Patent Document 7). However, since an additive is added to the liquid crystal, there is a possibility that the alignment of the liquid crystal may be adversely affected depending on the liquid crystal used.

[0006] JP 9-316200 JP 10-104633 JP 8-76128 JP 9-138414 JP 11-38415 WO 2016 / 194667 WO 2016 / 194668

[0007] When using materials containing silver for the electrodes and wiring of liquid crystal display elements, conventional liquid crystal alignment agents have the problem of silver migration. Using aluminum or nickel as a substitute for silver can improve this problem. However, there are problems such as a decrease in reflectivity when using aluminum or nickel for electrodes, and a decrease in electrical conductivity when using aluminum or nickel for wiring, leaving room for improvement.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a liquid crystal aligning agent that, when a silver-containing material is used as the electrodes and wiring of a liquid crystal display element, can suppress the migration of silver, suppress the migration of the silver-containing electrodes or wiring, and can obtain a liquid crystal alignment film that has a high voltage retention ratio even after being exposed to high temperatures for a long period of time; a liquid crystal alignment film obtained from the liquid crystal aligning agent; and a liquid crystal display element using the same.

[0009] As a result of intensive research to achieve the above object, the present inventors have found that a liquid crystal aligning agent containing a polymer having a specific compound as a constituent is extremely effective in achieving the above object, and have completed the present invention.

[0010] The present invention encompasses the following aspects: A liquid crystal aligning agent containing the following component (A) and a compound (B) represented by the following formula (1): Component (A): a polymer selected from the group consisting of polyimide precursors obtained by polymerizing a diamine component with a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides and derivatives thereof, and polyimides which are imidized products of the polyimide precursors, wherein the polymer (A) has a content of carboxy groups bonded to aromatic rings of 5 parts by mass or less per 100 parts by mass of the polymer. (A １ represents a monovalent group having a trialkoxysilyl group or a hydrogen atom. ２ each independently represents an alkyl group having 1 to 4 carbon atoms, a carboxy group, or a hydrogen atom.

[0011] According to the present invention, when a material containing silver is used as the electrodes and wiring of a liquid crystal display element, it is possible to provide a liquid crystal aligning agent that can suppress silver migration and obtain a liquid crystal alignment film that has a high voltage retention ratio even after being exposed to high temperatures for a long period of time, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element using the same.

[0012] It is generally known that coordination of a benzotriazole derivative to the surface of a silver-containing electrode or wiring forms a coating on the silver surface, thereby suppressing deterioration of the electrode or wiring. However, the present inventors have found that, depending on the properties of the polymer in contact with the silver-containing electrode or wiring, the coating can be destroyed, causing deterioration of the electrode or wiring. In response to this, the present inventors have found that by combining a polymer (A) containing a specific mass part or less of a carboxyl group bonded to an aromatic ring with a compound (B), it is possible to achieve both suppression of migration of the silver-containing electrode or wiring and the properties required for a liquid crystal alignment film.

[0013] Fig. 1 is a top view of a glass substrate having a silver pattern; Fig. 2 is a cross-sectional view of a silver pattern substrate on which a cured film has been formed; Fig. 3 is an enlarged view of a tip of the pattern after voltage application (pass); Fig. 4 is an enlarged view of a tip of the pattern after voltage application (fail).

[0014] Hereinafter, a liquid crystal aligning agent containing specific components, a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film will be described in detail, but the explanation of the constituent elements described below is an example of one embodiment of the present invention and is not intended to limit the scope of the present invention. In the following description, examples of "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. "Boc" represents a tert-butoxycarbonyl group, and "*" represents a bonding position.

[0015] <Polymer (A)> The liquid crystal aligning agent of the present invention contains the above-mentioned component (A). The term "polymer component" refers to a component consisting of a polymer, and may be composed of one type of polymer or multiple types of polymers. The polymer (A) may be one type or two or more types. The polymer (A) contained in the above-mentioned component (A) is a polymer selected from the group consisting of a polyimide precursor obtained by polymerizing a diamine component with a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides and their derivatives, and a polyimide (hereinafter also referred to as a polyimide-based polymer (A)). The polyimide precursor in the polyimide-based polymer (A) is obtained by polymerizing a diamine component with a tetracarboxylic acid derivative component. The tetracarboxylic acid derivative component contains at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides and their derivatives (hereinafter collectively referred to as a tetracarboxylic acid dianhydride-based compound). Examples of the polyimide precursor include polyamic acid and polyamic acid ester. Examples of the derivatives of the tetracarboxylic dianhydride include tetracarboxylic dihalides, tetracarboxylic dialkyl esters, and tetracarboxylic dialkyl ester dihalides.

[0016] <<Polyimide Polymer (A)>> When the polyimide polymer (A) is a polyamic acid, the polyimide polymer (A) can be obtained, for example, by polymerizing (polycondensing) a tetracarboxylic acid derivative component containing a tetracarboxylic acid dianhydride with a diamine component. The polyimide in the polyimide polymer (A) can be obtained by imidizing the polyamic acid. When the polyimide polymer (A) is a polyamic acid ester, the polyimide can be obtained by the method described below, and the polyimide can be obtained by imidizing the polyamic acid ester.

[0017] <<<Tetracarboxylic acid dianhydride compounds>>> Examples of the tetracarboxylic acid dianhydride compounds include aromatic tetracarboxylic acid dianhydrides, acyclic aliphatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and derivatives thereof. Here, the aromatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an aromatic ring. The acyclic aliphatic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, they do not necessarily have to be composed only of a chain hydrocarbon structure, and may partially contain an alicyclic structure or an aromatic ring structure.

[0018] Alicyclic tetracarboxylic acid dianhydrides are acid dianhydrides obtained by intramolecular dehydration of four carboxy groups, including at least one carboxy group bonded to an alicyclic structure. However, none of these four carboxy groups are bonded to an aromatic ring. Furthermore, they do not necessarily have to be composed solely of an alicyclic structure, and may partially contain a chain hydrocarbon structure or an aromatic ring structure.

[0019] Of the aromatic tetracarboxylic dianhydrides, acyclic aliphatic tetracarboxylic dianhydrides, and alicyclic tetracarboxylic dianhydrides, tetracarboxylic dianhydrides represented by the following formula (2) are preferred.

[0020] (X represents a structure selected from the group consisting of the following formulae (x-1) to (x-17) and (xr-1) to (xr-2).)

[0021]

[0022] (R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group; j and k are integers of 0 or 1; A １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, a phenylene group, a sulfonyl group, or an amide group. ２ may be the same or different. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.

[0023] Preferred specific examples of the tetracarboxylic acid dianhydride represented by the above formula (2) include those in which X is selected from the above formulas (x-1) to (x-8) and (x-10) to (x-11).

[0024] The above formula (x-1) is preferably one selected from the group consisting of the following formulae (x1-1) to (x1-6): X is preferably one selected from the group consisting of the following formulae (x1-1) to (x1-6) and the above formulae (x-5), (x-6) and (x-7).

[0025] (*1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.)

[0026] Preferred specific examples of the above formulae (xr-1) and (xr-2) include the following formulae (xr-3) to (xr-18).

[0027]

[0028]

[0029] The amount of the tetracarboxylic acid dianhydride represented by the formula (2) or a derivative thereof used in producing the polyimide polymer (A) is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, based on 1 mol of the total tetracarboxylic acid derivative components to be reacted with the diamine component.

[0030] <<<Diamine Component>>> The diamine component used in producing the polyimide precursor is not particularly limited. Examples of diamines are listed below, but the present invention is not limited to these. The above diamines may be used alone or in combination of two or more.

[0031] p-Phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 1,4-diamino-2,5-dimethoxybenzene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4-aminobenzylamine, 2-(4-aminophenyl)ethylamine, 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 2-(6-amino-2-naphthyl)ethylamine, 2,2'-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3-trifluoromethyl-4,4'-diaminobiphenyl, 2-trifluoromethyl-4,4'-diaminobiphenyl, 3-fluoro-4,4'-diaminobiphenyl, 2-fluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-biphenyl Bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, bis(4-aminophenoxy)methane, 1,2-bis(4- bis(aminophenyl)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-amino-2-methylphenyloxy)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12- Bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, 3-[2-[2-(4-aminophenoxy)ethoxy]ethoxy]benzenamine, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 4'-[2-(4-aminophenoxy)ethoxy]-[1,1'-biphenyl]-4-amine, 1,4-bis[2-(4-aminophenyl)ethyl]butanediol 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenyl diamines having a tetracarboxylic acid diimide structure such as N,N'-bis(4-aminophenyl)-cyclobutane-(1,2,3,4)-tetracarboxylic acid diimide, N,N'-bis(4-aminophenyl)-1,3-dimethylcyclobutane-(1,2,3,4)-tetracarboxylic acid diimide, and N,N'-bis(2,2'-bis(trifluoromethyl)-4'-amino-1,1'-biphenyl-4-yl)-cyclobutane-(1,2,3,4)-tetracarboxylic acid diimide;

[0032] 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 1,3-phenylenebis(4-aminobenzoate), 1,3-phenylenebis(3-aminobenzoate), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalate, bis(3-aminophenyl)isophthalate; 4,4'-diaminoazobenzene, diaminotolan, 4,4'-diaminochalcone, or [4-[(E)-3-[2-(2,4-diaminophenyl)ethoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate, or [4-[(E)-3-[[5-amino-2-[4- Diamines having a photoalignment group, such as aromatic diamines having a cinnamate structure, typified by amino-2-[[(E)-3-[4-[4-(4,4,4-trifluorobutoxy)benzoyl]oxyphenyl]prop-2-enoyl]oxymethyl]phenyl]phenyl]methoxy]-3-oxo-prop-1-enyl]phenyl]4-(4,4,4-trifluorobutoxy)benzoate; diamines having a photopolymerizable group at the terminal, such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone, 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl Diamines having a radical polymerization initiator function such as 3,5-diaminobenzoate; diamines having an amide bond such as 4,4'-diaminobenzanilide; diamines having a urea bond such as 1,3-bis(4-aminophenyl)urea; H ２ New York Ｄ -NH ２ (Y Ｄ represents a divalent organic group having, in the molecule, -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom); diamines having a thermally eliminable group such as

[0033] 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl) Silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 4,4'-diaminobenzophenone, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 1,4-bis(4-aminobenzyl)benzene;2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-piperazine, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N-[3-(1H-imidazol-1-yl)propyl] 3,5-Diaminobenzamide, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-4-methyl-2-oxazolyl]-benzenamine, 4-[4-[(4-aminophenoxy)methyl]-4,5-dihydro-2-oxazolyl]-benzenamine, 1,4-bis(p-aminobenzyl)piperazine, 4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)dianiline, 4-(4-aminophenoxycarboxamide), 4,4'-(1-methyl-1H-pyrrole-2,5-diyl)bis[benzenamine], 1,4-bis-(4-aminophenyl)-piperazine, 2-N-(4-aminophenyl)pyridine-2,5-diamine, 2-N-(5-aminopyridin-2-yl)pyridine-2,5-diamine, 2-(4-aminophenyl)-5-aminobenzimidazo heterocycle-containing diamines such as 2-(4-aminophenyl)-6-aminobenzimidazole, 5-(1H-benzimidazol-2-yl)benzene-1,3-diamine, or diamines represented by the following formulas (z-1) to (z-5), or 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenyl-N-methylamine, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-aminophenyl)-N,N diamines having at least one nitrogen atom-containing structure selected from the group consisting of nitrogen atom-containing heterocycles and secondary or tertiary amino groups (excluding amino groups derived from -N(D)- (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom)), typified by diamines having a diphenylamine structure such as N,N'-dimethylbenzidine or N,N'-bis(4-aminophenyl)-N,N'-dimethyl-1,4-benzenediamine;

[0034] 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl; 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 1,2-bis(4-aminophenyl)ethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dica diamines having a carboxy group such as carboxylic 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, 4,4'-diaminodiphenylether-3,3'-dicarboxylic acid; 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, ... diamines having a steroid skeleton such as cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-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 represented by the following formulae (V-1) to (V-2); 1,3-bis(3-aminobenzoyloxy)cholestane diamines having a siloxane bond, such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; alicyclic diamines, such as 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4'-methylenebis(cyclohexylamine); and diamines in which two amino groups are bonded to a group represented by any one of formulas (Y-1) to (Y-167) described in WO2018 / 117239.

[0035]

[0036] (In formula (V-1), m and n each represent an integer of 0 to 3 (provided that 1≦m+n≦4 is satisfied), j represents an integer of 0 or 1, and X １ is -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ３ )-, -NH-, -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—. １ represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms. ２ is -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—; R ２ represents an alkyl group having 3 to 30 carbon atoms or a fluorine atom-containing alkyl group having 3 to 20 carbon atoms. １ , and R １ When two occur, each independently has the above definition.

[0037] It should be noted that D in -N(D)- contained in the above diamine is preferably a carbamate-based protecting group typified by a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, Boc, etc. Boc is particularly preferred from the viewpoints that it is efficiently eliminated by heat, is eliminated at a relatively low temperature, and is discharged as a harmless gas upon elimination.

[0038] Preferred examples of the diamine having a thermally detachable group exemplified above are diamines selected from the following formulae (d-1) to (d-7). (In formulas (d-2), (d-6), and (d-7), R represents a hydrogen atom or Boc.)

[0039] When a diamine having the thermally detachable group is used as the diamine component used in the production of a polyimide precursor, the amount of the thermally detachable group is preferably 5 to 40 mol %, more preferably 5 to 35 mol %, and even more preferably 5 to 30 mol %, per mol of the diamine component, from the viewpoint of suitably achieving the effects of the present invention.

[0040] From the viewpoint of reducing afterimages resulting from residual DC or enhancing electrical properties, the polymer (A) may contain at least one polymer selected from the group consisting of polyimide precursors obtained using a diamine component containing the diamine having a nitrogen atom-containing structure and imidized products of the polyimide precursors (hereinafter also referred to as polyimide polymer (Q)).

[0041] Examples of the tetracarboxylic acid derivative component for obtaining the polyimide polymer (Q) include tetracarboxylic acid derivative components containing the tetracarboxylic acid dianhydride compounds described above. Among the tetracarboxylic acid dianhydride compounds for obtaining the polyimide polymer (Q), the tetracarboxylic acid dianhydride represented by the formula (2) or a derivative thereof is preferred. The amount of the tetracarboxylic acid dianhydride represented by the formula (2) or a derivative thereof used is preferably 10 mol % or more, more preferably 20 mol % or more, based on 1 mol of the total tetracarboxylic acid derivative components to be reacted with the diamine component.

[0042] The amount of the diamine having a nitrogen atom-containing structure used as the diamine component for obtaining the polyimide polymer (Q) is preferably 5 to 100 mol %, more preferably 10 to 95 mol %, and even more preferably 20 to 80 mol %, based on the total amount of the diamine components for obtaining the polymer (Q).

[0043] The diamine component for obtaining the polyimide polymer (Q) may further contain a diamine other than the diamine having a nitrogen atom-containing structure. A more preferred example is a diamine having at least one group selected from the group consisting of a urea bond, an amide bond, a carboxy group, and a hydroxy group in the molecule (hereinafter also referred to as diamine (c)). The amount of diamine (c) used is preferably 1 to 95 mol %, more preferably 5 to 90 mol %, and even more preferably 20 to 80 mol %, based on the total amount of the diamine component for obtaining the polymer (Q).

[0044] In the polymer (A) of the present invention, the content of carboxy groups bonded to the aromatic rings is 5 parts by mass or less per 100 parts by mass of the polymer. The carboxy groups bonded to the aromatic rings may be derived from a tetracarboxylic dianhydride or a derivative thereof contained in the tetracarboxylic acid derivative component, or may be derived from a diamine contained in the diamine component. The content of carboxy groups bonded to the aromatic rings is preferably 3 parts by mass or less, more preferably 1 part by mass or less, per 100 parts by mass of the polymer. Note that since the polymer (A) of the present invention is a polymer having a carboxy group content bonded to the aromatic rings of 5 parts by mass or less per 100 parts by mass of the polymer, the tetracarboxylic dianhydride and diamine must be selected so as to provide a polymer that satisfies these conditions. Furthermore, even when a polyimide-based polymer (Q) is contained, the content of carboxy groups bonded to the aromatic rings of the polymer (Q) must be 5 parts by mass or less per 100 parts by mass of the polymer.

[0045] The component (A) contained in the liquid crystal aligning agent of the present invention may be a mixture of the polyimide polymer (Q) and at least one polymer selected from the group consisting of polyimide precursors obtained using a diamine component that does not contain the diamine having a nitrogen atom-containing structure and imidized products of the polyimide precursor (hereinafter also referred to as polyimide polymer (H)). The content ratio of the polyimide polymer (Q) to the polyimide polymer (H), expressed as a mass ratio of [polyimide polymer (Q)] / [polyimide polymer (H)], is preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, and even more preferably 30 / 70 to 70 / 30.

[0046] The component (A) contained in the liquid crystal aligning agent of the present invention may contain a polymer other than the polymer (A). Specific examples of the other polymer include a polymer selected from the group consisting of polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and poly(meth)acrylate. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, and SMA3000 (manufactured by Cray Valley Corporation), and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.). A specific example of poly(isobutylene-maleic anhydride) copolymers includes ISOBAN-600 (manufactured by Kuraray Co., Ltd.). A specific example of poly(vinyl ether-maleic anhydride) copolymers includes Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation). One type of other polymer may be used alone, or two or more types may be used in combination. The content ratio of the other polymer is more preferably 0.1 to 90 parts by mass, and even more preferably 1 to 90 parts by mass, per 100 parts by mass of component (A) contained in the liquid crystal aligning agent.

[0047] <Method for Producing Polyimide Precursor> Polyamic acid, which is one of the polyimide precursors, can be produced by the following method. Specifically, it can be synthesized by reacting (polycondensation reaction) a tetracarboxylic acid derivative component containing a tetracarboxylic acid dianhydride with the above-mentioned diamine component in the presence of an organic solvent, preferably at −20 to 150° C., more preferably at 0 to 50° C., for preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

[0048] Specific examples of organic solvents used in the above reaction 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. Furthermore, when the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, or diethylene glycol monoethyl ether can be used. These solvents may be used in combination of two or more.

[0049] The reaction can be carried out at any concentration, 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 additional solvent added later. In the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic acid derivative components is preferably 0.8 to 1.2. As with a typical polycondensation reaction, the closer this molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

[0050] The polyamic acid obtained by the above reaction can be precipitated and recovered by pouring the reaction solution into a poor solvent while stirring it thoroughly. Alternatively, the precipitation can be repeated several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polyamic acid powder. The poor solvent is not particularly limited, but examples include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.

[0051] Polyamic acid esters, which are one type of polyimide precursors, can be produced by known methods such as (1) a method of esterifying the above-mentioned polyamic acid, (2) a method of reacting a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester dichloride with a diamine component, and (3) a method of polycondensing a tetracarboxylic acid derivative component containing a tetracarboxylic acid diester with a diamine.

[0052] The polyamic acid and polyamic acid ester may be end-modified polymers obtained by using an appropriate end-capping agent together with the tetracarboxylic acid derivative component and diamine component as described above during production. Examples of the end-capping agent include acid monoanhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; 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, and the like. Examples of suitable terminal blocking agents include monoamine compounds such as 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine; monoisocyanate compounds such as isocyanates having unsaturated bonds, 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. The proportion of the terminal blocking agent used is preferably 40 parts by mole or less, and more preferably 30 parts by mole or less, per 100 parts by mole of the total of the diamine components used.

[0053] <Method for Producing Polyimide> The polyimide used in the present invention can be produced by imidizing the above-mentioned polyimide precursor by a known method. In the polyimide, the ring closure rate (also referred to as the imidization rate) of the functional group of the polyamic acid or polyamic acid ester does not necessarily need to be 100% and can be adjusted as desired depending on the application and purpose.

[0054] Methods for obtaining polyimide by imidizing the polyamic acid or polyamic acid ester include thermal imidization in which a solution of the polyamic acid or polyamic acid ester is heated as is, and catalytic imidization in which a catalyst (e.g., a basic catalyst such as pyridine, or an acid anhydride such as acetic anhydride) is added to a solution of the polyamic acid or polyamic acid ester.

[0055] <Solution Viscosity and Molecular Weight of Polymer> The polyamic acid, polyamic acid ester, and polyimide used in the present invention preferably have a solution viscosity of, for example, 10 to 1,000 mPa·s when prepared into a solution of 10 to 15% by 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% by mass prepared using a good solvent for the polymer (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.).

[0056] The polystyrene-equivalent weight average molecular weight (Mw) of the polyamic acid, polyamic acid ester, and polyimide, as measured by gel permeation chromatography (GPC), is preferably 1,000 to 500,000, and more preferably 2,000 to 500,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, and more preferably 10 or less. With the molecular weight in this range, good liquid crystal alignment properties can be ensured in liquid crystal display elements.

[0057] <<<<Compound (B)>>> The liquid crystal aligning agent of the present invention contains the compound (B) represented by the above formula (1). One type of compound (B) may be used, or two or more types of compound (B) may be used. In the compound (B), A ２ At least one of A may represent a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a carboxy group. １ may have a carboxy group. １ may be a monovalent group represented by "AX-*" (A represents a trialkoxysilyl group, X represents -(CH ２ ) ｎ -(n is an integer of 1 to 18), or the -(CH ２ ) ｎ -of-CH ２ - at least a part of - to -CONH-, -NHCO-, -CO-N(CH ３ ) represents a group in which any hydrogen atom in X is replaced by any of -, -NH-, -O-, -COO-, or -OCO-. Any hydrogen atom in X may be substituted by a halogen atom, a carboxy group, a hydroxy group, a cyano group, or a nitro group.

[0058] Preferred compounds represented by the formula (1) above include benzotriazole, benzotriazole derivatives substituted with an alkyl group having 1 to 4 carbon atoms, such as 4-methylbenzotriazole and 5-methylbenzotriazole, and benzotriazole derivatives having a monovalent group with a trialkoxysilyl group, such as N-(trimethoxysilylpropyl)-1H-benzotriazole-1-carbodiamide. Among these, the compounds represented by the following formulae (b-1) to (b-4) are more preferred.

[0059] The content of the compound (B) 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 1 to 10 parts by mass, relative to 100 parts by mass of the component (A).

[0060] <Liquid Crystal Alignment Agent> The liquid crystal aligning agent is used to prepare a liquid crystal alignment film and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing the above-mentioned component (A), compound (B), and a solvent. The content (concentration) of the polymer component contained in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the thickness of the coating film to be formed. However, from the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. From the viewpoint of optimally obtaining the effects of the present invention, the total content of the polymer (A) in the liquid crystal aligning agent is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 50 parts by mass or more, relative to the total 100 parts by mass of the polymer components contained in the liquid crystal aligning agent (p).

[0061] The solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can uniformly dissolve the polymer component. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and methyl ethyl ketone. Examples of suitable good solvents include propanamide, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone (collectively referred to as "good solvents"). Among these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and γ-butyrolactone are preferred. The content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass of the total solvent contained in the liquid crystal aligning agent.

[0062] In addition, the solvent contained in the liquid crystal aligning agent is preferably a mixed solvent containing, in addition to the above solvent, a solvent (also called a poor solvent) that improves the coatability when applying the liquid crystal aligning agent and the surface smoothness of the coating film. Specific examples of the poor solvent to be used in combination are listed below, but are not limited thereto.

[0063] For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, propylene glycol diacetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like can be mentioned. The content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvent contained in the liquid crystal aligning agent.The type and content of the poor solvent are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0064] Of these, diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, or diisobutyl ketone is preferred.

[0065] Preferred solvent combinations of a good solvent and a poor solvent include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, and N-methyl-2-pyrrolidone and γ- butyrolactone, propylene glycol monobutyl ether, and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether, and diisobutyl carbinol; N-methyl-2-pyrrolidone, γ-butyrolactone, and dipropylene glycol dimethyl ether; and N-methyl-2-pyrrolidone, propylene glycol monobutyl ether, and dipropylene glycol dimethyl ether.

[0066] The liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the solvent (hereinafter also referred to as additive components). Examples of such additive components include a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as crosslinking compound), an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealing agent, a dielectric or conductive substance for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film, a stabilizer for improving the stability of the varnish, a surfactant or antifoaming agent for adjusting the surface tension of the varnish, etc.

[0067] Examples of the crosslinkable compound include at least one crosslinkable compound selected from the group consisting of a crosslinkable compound (c-1) having at least one substituent selected from an epoxy group, an oxetanyl group, an oxazoline structure, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and a crosslinkable compound (c-2) having a polymerizable unsaturated group. Specific preferred examples of the crosslinkable compounds (c-1) and (c-2) include the following compounds: Examples of compounds having an epoxy group include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, bisphenol A epoxy resins such as Epikote 828 (manufactured by Mitsubishi Chemical Corporation), bisphenol F epoxy resins such as Epikote 807 (manufactured by Mitsubishi Chemical Corporation), and hydrogenated bisphenols such as YX-8000 (manufactured by Mitsubishi Chemical Corporation). phenol A type epoxy resins, biphenyl skeleton-containing epoxy resins such as YX6954BH30 (manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resins such as EPPN-201 (manufactured by Nippon Kayaku Co., Ltd.), (o, m, p-) cresol novolac type epoxy resins such as EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.), compounds in which a tertiary nitrogen atom is bonded to an aromatic carbon atom such as tetrakis(glycidyloxymethyl)methane, N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4.4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane;N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N-diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl) ) cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, 1,3,5-tris(N,N-diglycidylaminomethyl)benzene and other compounds in which a tertiary nitrogen atom is bonded to an aliphatic carbon atom; isocyanurate compounds such as triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.); compounds described in paragraph

[0037] of JP-A-10-338880 and compounds described in WO2017 / 170483; Examples of compounds having an oxetanyl group include 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (Aron Oxetane OXT-121 (XDO)), bis[2-(3-oxetanyl)butyl]ether (Aron Oxetane OXT-221 (DOX)), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene (CTOX), and compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO2011 / 132751; Examples of compounds having an oxazoline structure include compounds such as 2,2'-bis(2-oxazoline) and 2,2'-bis(4-methyl-2-oxazoline), polymers and oligomers having an oxazoline group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.), and compounds described in paragraph

[0115] of Japanese Patent Application Laid-Open No. 2007-286597;Examples of compounds having a cyclocarbonate group include N,N,N',N'-tetra[(2-oxo-1,3-dioxolan-4-yl)methyl]-4,4'-diaminodiphenylmethane, N,N',-di[(2-oxo-1,3-dioxolan-4-yl)methyl]-1,3-phenylenediamine, and the compounds described in paragraphs

[0025] to

[0030] and

[0032] of WO2011 / 155577; Examples of compounds having a blocked isocyanate group include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, and Millionate MS-50 (all manufactured by Tosoh Corporation), Takenate B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.), compounds having two or more blocked isocyanate groups described in paragraphs

[0046] to

[0047] of Japanese Patent Application Laid-Open No. 2014-224978, and compounds having three or more blocked isocyanate groups described in paragraphs

[0119] to

[0120] of WO2015 / 141598; Examples of compounds having a hydroxy group and / or an alkoxy group include N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane, compounds described in WO2015 / 072554, paragraph

[0058] of JP2016-118753A, compounds described in JP2016-200798A, and compounds described in WO2010 / 074269A;Examples of crosslinkable compounds having a polymerizable unsaturated group include glycerin mono(meth)acrylate, glycerin di(meth)acrylate (1,2-, 1,3-mixture), glycerin tris(meth)acrylate, glycerol 1,3-diglycerolate di(meth)acrylate, pentaerythritol tri(meth)acrylate, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, pentaethylene glycol mono(meth)acrylate, and hexaethylene glycol mono(meth)acrylate;

[0068] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above are disclosed on pages 53

[0105] to 55

[0116] of WO2015 / 060357. Two or more types of crosslinkable compounds may be combined.

[0069] When a crosslinkable compound is used, the content of the crosslinkable compound in the liquid crystal aligning agent is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0070] Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl N-trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-3-triethoxysilylpropyltriethylenetetramine, N-3-trimethoxysilylpropyltriethylenetetramine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N -benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimeth Examples of silane coupling agents include silane coupling agents such as dimethylsilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(3-trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.When an adhesion aid is used, the content of the adhesion aid in the liquid crystal aligning agent is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0071] A stabilizer may be added to the composition of the present invention in order to improve the stability of the varnish. Specific examples of the stabilizer include the polyol compounds described in WO 2011 / 129414 and the amine compounds described in WO 2021 / 171939.

[0072] A surfactant or antifoaming agent may be added to the composition of the present invention in order to adjust the surface tension of the varnish, and any commonly known surfactant may be used as long as it does not separate from the polymer, solvent, etc. As the surfactant, for example, a cationic surfactant, an anionic surfactant, or a nonionic surfactant may be used, with nonionic surfactants being more preferred.

[0073] Specific examples of nonionic surfactants (hereinafter referred to as trade names) include Megafac (registered trademark) F-251, F-253, F-281, F-430, F-477, F-551, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F-565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, and R-41. , R-94, RS-56, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90, DS-21 (manufactured by DIC Corporation), FC-4432 (manufactured by Sumitomo 3M Limited), Surflon (registered trademark) S-242, S-243, S-420, S-431, S-386, S-611, S-647, S-651, S-653, S-656, S-658, S-693, S-CFJ (manufactured by Asahi Glass Co., Ltd.), and the like, but are not limited thereto.

[0074] As the defoaming agent, silicone-based defoaming agents, acrylic polymer-based defoaming agents, vinyl ether polymer-based defoaming agents, etc. can be used, but are not limited to these.

[0075] Specific examples of the defoaming agent include KF-96, KF-6701, KS-7708, KS-66, KS-69, KS-7716, KS-602A, FA-600, X-50-1110D, and KM-601S (manufactured by Shin-Etsu Silicone Co., Ltd.), FLORENE AC-230, AC-262H, AC-300, AC-303, AC-326F, AO-106, AO-108, and AO-108AF (manufactured by Kyoeisha Chemical Co., Ltd.), BYK-051N, BYK-052N, BYK-053N, BYK-054, BYK-055, BYK-057, BYK-070, BYK-072, BYK-077, BYK-081, and BYK-091. K-085, BYK-141, BYK-1681, BYK-1692SD, BYK-1709, BYK-1751, BYK-1752, BYK-1758, BYK-1759, BYK-1760, BYK-1795, BYK-1796, BYK-1797, BYK-1799, BYK-A500, BYK-A501BYK-A505, BYK-A506, BYK-A515, BYK-A525, BYK-A530, BYK-A535, BYK-A550, BYK-A555, BYK-A560 (manufactured by BYK Japan Co., Ltd.), and the like, but are not limited thereto.

[0076] The surfactants and antifoaming agents may be used either individually or in combination, and the amount added is preferably 5 parts by mass or less per 100 parts by mass of the polymer.

[0077] (Liquid crystal alignment film) The liquid crystal alignment film of the present invention is formed using the liquid crystal aligning agent of the present invention. The method for producing a liquid crystal alignment film of the present invention includes, for example, applying the liquid crystal aligning agent to a substrate, baking the applied liquid crystal aligning agent, and irradiating the resulting film with polarized radiation. A preferred embodiment of the method for producing a liquid crystal alignment film of the present invention includes, for example, a method for producing a liquid crystal alignment film including a step of applying the liquid crystal aligning agent to a substrate (step (1)), a step of baking the applied liquid crystal aligning agent (step (2)), and, optionally, a step of performing an alignment treatment on the film obtained in step (2) (step (3)).

[0078] <Step (1)> The substrate to which the liquid crystal aligning agent used in the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and glass substrates, silicon nitride substrates, acrylic substrates, polycarbonate substrates, and other plastic substrates can also be used. In this case, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving the liquid crystal is formed, from the viewpoint of simplifying the process. Furthermore, in a reflective liquid crystal display element, an opaque material such as a silicon wafer can be used for only one substrate, and in this case, a light-reflecting material such as silver, aluminum, nickel, or an alloy containing any of the above metals can also be used for the electrode.

[0079] 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.

[0080] <Step (2)> Step (2) is a step of baking the liquid crystal aligning agent applied to the substrate to form a film. After applying the liquid crystal aligning agent to the substrate, the solvent can be evaporated or the amic acid or amic acid ester in the polymer can be thermally imidized using a heating means such as a hot plate, a heat circulation oven, or an IR (infrared) oven. The drying and baking steps after applying the liquid crystal aligning agent of the present invention can be performed at any temperature and for any time, and may be performed multiple times. The temperature for evaporating the solvent of the liquid crystal aligning agent can be, for example, 40 to 180°C. From the perspective of shortening the process, it can also be performed at 40 to 150°C. The baking time is not particularly limited, but can be 1 to 10 minutes or 1 to 5 minutes. When thermally imidizing the amic acid or amic acid ester in the polymer, a baking step can be performed at a temperature range of, for example, 150 to 300°C or 150 to 250°C after the solvent evaporation step. The baking time is not particularly limited, but may be 5 to 40 minutes or 5 to 30 minutes. If the baked film is too thin, the reliability of the liquid crystal display element may decrease, so the thickness is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0081] <Step (3)> Step (3) is a step of optionally performing an alignment treatment on the film obtained in step (2). In a horizontal electric field type liquid crystal display element such as an IPS mode or an FFS mode, an alignment ability is imparted to the formed coating film by performing an alignment ability imparting treatment. In a vertical alignment type liquid crystal display element such as a VA mode or a PSA mode, the formed coating film can be used as a liquid crystal alignment film as is, but the coating film may also be subjected to an alignment ability imparting treatment. The alignment treatment method for the liquid crystal alignment film may be a rubbing treatment method or a photo-alignment treatment method. Examples of the photo-alignment treatment method include, but are not limited to, a method in which the surface of the film-like material is irradiated with polarized radiation in a certain direction and, if necessary, subjected to a heat treatment to impart liquid crystal alignment (also referred to as liquid crystal alignment ability).

[0082] The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention. From the viewpoint of obtaining high liquid crystal alignment properties, the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film for a vertical alignment type liquid crystal display element such as a VA type or a PSA type, but is not particularly limited thereto.

[0083] A liquid crystal display element can be produced by obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention, preparing a liquid crystal cell by a known method, and arranging liquid crystals in the liquid crystal cell. Specifically, the following two methods can be mentioned.

[0084] In the first method, two substrates are placed opposite each other with a gap (cell gap) between them so that their liquid crystal alignment films face each other, and then the peripheries of the two substrates are bonded together using a sealant. A liquid crystal composition is injected into the substrate surfaces and the cell gap defined by the sealant so that it comes into contact with the film surface, and the injection hole is then sealed.

[0085] The second method is called the ODF (One Drop Fill) method. For example, a UV-curable sealant is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed, and a liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film surface. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with UV light to cure the sealant.

[0086] In either the first or second method, it is desirable to further heat the coating film to a temperature at which the liquid crystal composition is in an isotropic phase, and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling. When rubbing treatment is performed on the coating film, the two substrates are positioned opposite each other so that the rubbing directions of the coating films are at a predetermined angle, for example, perpendicular or antiparallel. Similarly, when photoalignment treatment is performed, the substrates are positioned opposite each other so that the alignment directions are at a predetermined angle, for example, perpendicular or antiparallel. Examples of sealing agents that can be used include epoxy resins containing a curing agent and aluminum oxide spheres as spacers. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred.

[0087] The liquid crystal material may be either a positive type or a negative type, but is preferably a negative type.

[0088] 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 the compounds used below are as follows.

[0089] (Organic solvent) NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve (Diamine) DA-1 to DA-5: Compounds represented by the following formulas (DA-1) to (DA-5), respectively (Tetracarboxylic acid dianhydride) DAH-1 to DAH-4: Compounds represented by the following formulas (DAH-1) to (DAH-4), respectively (Benzotriazole additive) B-1 to B-2: Compounds represented by the following formulas (B-1) to (B-2), respectively (Crosslinking agent) C-1: Compound represented by the following formula (C-1) (Stabilizer) D-1 to D-2: Compounds represented by the following formulas (D-1) to (D-2), respectively (Surfactant) E-1: F-563 (DIC Corporation, nonionic fluorine-containing group / lipophilic group-containing oligomer) (Other additives) F-1 to F-4: Compounds represented by the following formulas (F-1) to (F-4), respectively

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096] <Measurement of Imidization Ratio> A polyimide powder was dissolved in NMP to prepare a solution with a solid content of 8% by mass, and 0.38 g of the NMP solution was weighed. ６1.0 mL of a mixture of 100% TMS and 0.05% TMS was added to the solution, homogenized, and placed in an NMR sample tube (Kusano Scientific NMR Sampling Tube Standard, φ5). 500 MHz proton NMR was measured using a JEOL Datum NMR analyzer (JNW-ECA500). The imidization ratio was calculated using the integrated peak value of this proton and the integrated peak value of the proton derived from the NH group of the amic acid, which appeared around 9.5 to 10.0 ppm, according to the following formula: In the formula, x represents the integrated peak value of the proton derived from the NH group of the amic acid, y represents the integrated peak value of the reference proton, and α represents the ratio of the number of reference protons to one proton of the NH group of the amic acid in the case of polyamic acid (with an imidization ratio of 0%). Imidization ratio (%) = (1 - α x / y) x 100

[0097] <Calculation of the content ratio of carboxy groups bonded to aromatic rings (hereinafter also referred to as aromatic carboxy groups) in a polymer> The content ratio of aromatic carboxy groups in a polymer was calculated by focusing on the mass ratio of carboxy group sites in an aromatic carboxy group-containing compound. For example, when a polyamic acid containing only the partial structure of DA-5 as the aromatic carboxy group is used as a polymer component, the calculation was performed using the following formula: Ratio of aromatic carboxy groups in polymer [%] = Molecular weight of carboxy groups (45.0) × Content ratio of DA-5 in total amount of diamine ÷ (Average molecular weight of acid dianhydride monomer + Average molecular weight of diamine monomer)

[0098] <Production Examples> (Production Example 1) DA-1 (15.22 g, 40 mmol) was added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, followed by the addition of NMP (74.3 g) and dissolution with stirring while supplying nitrogen. DAH-1 (7.72 g, 39 mmol) was added to this diamine solution while stirring, followed by the addition of NMP (17.4 g), and the mixture was further stirred at 40°C for 20 hours to obtain a polyamic acid solution (PAA-1) with a solids concentration of 20 mass%.

[0099] (Production Example 2) 30 g (10.4 mmol) of polyamic acid solution PAA-1 was placed in a 100 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and 36.7 g of NMP was added to adjust the solids concentration to 9% by mass, followed by stirring for 30 minutes. 2.3 g of acetic anhydride (2.2 equivalents relative to the molar amount of polyamic acid) and 0.4 g of pyridine (0.5 equivalents relative to the molar amount of polyamic acid) were added to the resulting polyamic acid solution, and the mixture was stirred at room temperature for 30 minutes, then heated at 55 ° C. for 4 hours to perform chemical imidization. The resulting reaction solution was poured into 300 mL of methanol with stirring, and the precipitate was filtered off. The same procedure was repeated twice to wash the resin powder, and then dried at 100 ° C. for 8 hours to obtain a polyimide resin powder. 5.0 g of the obtained polyimide resin powder was placed in a 100 mL Erlenmeyer flask, NMP was added to a solids concentration of 8%, and the mixture was stirred at 50°C for 24 hours to dissolve the polyimide resin, yielding a polyimide solution (PI-1-a). The imidization rate of the polyimide resin was 85%.

[0100] (Production Example 3) Using 30 g (10.4 mmol) of PAA-1, a polyimide solution (PI-1-b) was obtained in the same manner as in Production Example 2. However, the solids concentration during chemical imidization was 6.5 mass %, 2.7 g of acetic anhydride (2.5 molar equivalents relative to polyamic acid) and 1.6 g of pyridine (2.0 molar equivalents relative to polyamic acid) were used, and the heating conditions were 50°C and 2 hours. The imidization rate of the obtained polyimide resin was 81%.

[0101] (Production Example 4) Using 30 g (10.4 mmol) of PAA-1, a polyimide solution (PI-1-c) was obtained in the same manner as in Production Example 3. However, the heating conditions were 50°C for 1 hour and 45 minutes. The imidization rate of the obtained polyimide resin was 74%.

[0102] (Production Example 5) Using 30 g (10.4 mmol) of PAA-1, a polyimide solution (PI-1-d) was obtained in the same manner as in Production Example 3. However, the heating conditions were 50°C for 1 hour and 30 minutes. The imidization rate of the obtained polyimide resin was 63%.

[0103] (Production Example 6) Using 30 g (10.4 mmol) of PAA-1, a polyimide solution (PI-1-e) was obtained in the same manner as in Production Example 3. However, the heating conditions were 50°C and 1 hour. The imidization rate of the obtained polyimide resin was 54%.

[0104] (Production Example 7) DA-1 (9.51 g, 25 mmol) and DA-2 (2.70 g, 25 mmol) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and then NMP (28.5 g) was added and stirred while sending nitrogen to dissolve. DAH-2 (2.24 g, 10 mmol) was added while stirring this diamine solution, and NMP (15.7 g) was added, and then the mixture was stirred for 3 hours at 60 ° C. The solution was cooled to room temperature, and DAH-1 (7.75 g, 39.5 mmol) was added while stirring, and NMP (45.7 g) was added, and the mixture was further stirred at 40 ° C. for 12 hours to obtain a polyamic acid solution (PAA-2) with a solids concentration of 20% by mass.

[0105] (Production Example 8) Using 10 g (4.4 mmol) of PAA-2, a polyimide solution (PI-2) was obtained in the same manner as in Production Example 3. However, the amount of acetic anhydride used for chemical imidization was 2.3 g (5.0 molar equivalents relative to the polyamic acid) and the amount of pyridine used was 0.7 g (2.0 molar equivalents relative to the polyamic acid), and the heating conditions were 50°C and 3 hours. The imidization rate of the obtained polyimide resin was 75%.

[0106] (Production Example 9) DA-1 (9.51 g, 25 mmol) and DA-2 (2.70 g, 25 mmol) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and then NMP (28.5 g) was added and stirred while sending nitrogen to dissolve. DAH-3 (2.50 g, 10 mmol) was added while stirring this diamine solution, and NMP (15.7 g) was added, and then the mixture was stirred at 80 ° C. for 5 hours. The solution was cooled to room temperature, and DAH-1 (7.75 g, 39.5 mmol) was added while stirring, and NMP (45.7 g) was added, and the mixture was further stirred at 40 ° C. for 12 hours to obtain a polyamic acid solution (PAA-3) with a solids concentration of 20% by mass.

[0107] (Production Example 10) Using 10 g (4.4 mmol) of PAA-3, a polyimide solution (PI-3) was obtained in the same manner as in Production Example 3. However, the amount of acetic anhydride used for chemical imidization was 2.3 g (5.0 molar equivalents relative to the polyamic acid) and the amount of pyridine used were 0.9 g (2.5 molar equivalents relative to the polyamic acid), and the heating conditions were 60°C and 4 hours. The imidization rate of the obtained polyimide resin was 81%.

[0108] (Production Example 11) DA-3 (3.89 g, 36 mmol) and DA-4 (1.39 g, 4 mmol) were placed in a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, followed by the addition of NMP (25.8 g) and dissolution with stirring while supplying nitrogen. DAH-4 (11.77 g, 39.2 mmol) was added to this diamine solution while stirring, and then NMP (42.4 g) was added, followed by further stirring at room temperature for 20 hours to obtain a polyamic acid solution (PAA-4) with a solids concentration of 20 mass%.

[0109] (Production Example 12) Using 10 g of PAA-4, chemical imidization was carried out by a known method. The obtained powder was dissolved in NMP to obtain a polyimide solution (PI-4) with a solid content concentration of 8 mass %. The imidization rate of the obtained polyimide resin was 88%.

[0110] (Production Example 13) DA-1 (4.57 g, 12 mmol) and DA-5 (4.26 g, 28 mmol) were added to a 200 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube, and then NMP (43.1 g) was added and stirred while sending nitrogen to dissolve. DAH-3 (7.51 g, 30 mmol) was added while stirring this diamine solution, and NMP (5.9 g) was added, and then the mixture was stirred at 80 ° C. for 5 hours. The solution was cooled to room temperature, and DAH-1 (1.88 g, 9.6 mmol) was added while stirring, and NMP (23.9 g) was added, and the mixture was further stirred at 40 ° C. for 12 hours to obtain a polyamic acid solution (PAA-5) with a solids concentration of 20% by mass.

[0111] (Production Example 14) Using 10 g of PAA-5, chemical imidization was carried out by a known method. The obtained powder was dissolved in NMP to obtain a polyimide solution (PI-5) with a solid content concentration of 8 mass %. The imidization rate of the obtained polyimide resin was 81%.

[0112] Example 1 The polyimide solution (PI-1-a) obtained in Synthesis Example 1, NMP, and BCS were added to a sample tube containing a stirring bar, and additives B-1 and C-1 were added in amounts of 6 parts by mass and 3 parts by mass, respectively, relative to 100 parts by mass of polymer solid content, followed by stirring for 30 minutes. After stirring, a liquid crystal aligning agent (A1) was obtained in which the solid content concentration of the polyimide solution (PI-1-a) was 4.5% by mass and the solvent composition was NMP:BCS=60:40 by mass ratio.

[0113] Examples 2 to 12, Comparative Examples 1 to 9 Liquid crystal aligning agents (A2) to (A12) and (X1) to (X9) were obtained in the same manner as in Example 1, except that the types and amounts of the polymer components and additives used were changed as shown in the following Table 1. The numerical values ​​(B) to (F) in Table 1 each represent the blending ratio (parts by mass) of the additive relative to a total of 100 parts by mass of the polymer component (A) used in the preparation of the liquid crystal aligning agent.

[0114] <Preparation of Sample for Evaluating Migration Resistance> A silver pattern 2 as shown in Figure 1 was prepared on a glass substrate 1 by vapor deposition. The silver thickness was 100 nm. Varnishes of liquid crystal alignment agents (A1) to (A12) and (X1) to (X9) were spin-coated onto the glass substrate with the silver pattern, and the substrate was first pre-baked at 80°C for 2 minutes. This was then post-baked at 120°C for 5 minutes to prepare a liquid crystal alignment film 3 with a thickness of approximately 300 nm. Conductive tape 4 was attached to both ends of the electrode to obtain a sample for evaluation. A cross-sectional view of the silver pattern substrate on which the cured film was formed is shown in Figure 2. The obtained sample was subjected to an evaluation of migration resistance using the following method.

[0115] <Evaluation of Migration Resistance> The migration resistance evaluation sample prepared above was placed under conditions of a temperature of 85°C and a relative humidity of 85% RH, and a test was conducted in which an anode and a cathode were connected to both ends of the silver pattern, and a voltage of 50 V was applied for 50 hours so that an electric field would concentrate at the tip of the pattern, and the occurrence of migration as a result of this test was confirmed. The occurrence of migration was confirmed by observing the tip of the pattern with a microscope after the test. The patterns after the test are shown in Figures 3 and 4. The evaluation was performed by defining "◯" when no deposition was observed after voltage application as in Figure 3, and "X" when deposition occurred as in Figure 4.

[0116] <Preparation of Liquid Crystal Display Element> The resulting liquid crystal alignment agent was spin-coated onto the ITO surface of a glass substrate with a transparent electrode composed of an ITO film. The substrate was then dried on a hot plate at 80°C for 2 minutes and then baked on a hot plate at 120°C for 5 minutes, yielding a substrate with a 100 nm-thick liquid crystal alignment film. Two of these substrates with liquid crystal alignment films were prepared and rubbed so that the alignment direction would be 180° after lamination. A rayon cloth (YA-20R, manufactured by Yoshikawa Chemical Co., Ltd.) with a roll diameter of 120 mm was used for the rubbing. The rubbing was performed at a rotation speed of 1000 rpm, a movement speed of 25 mm / sec, and a pressing depth of 0.3 mm. After rubbing, the substrate was ultrasonically cleaned in pure water for 1 minute and dried at 80°C for 15 minutes. After rubbing, 6 μm bead spacers were sprayed on the liquid crystal alignment film on one of the substrates, and a sealant (XN-1500T, manufactured by Mitsui Chemicals) was applied in a shape that left a liquid crystal injection port. Next, the other substrate was attached so that the liquid crystal alignment film faces each other and the alignment direction is 180°. After that, the substrate was heated at 80°C for 15 minutes, then at 100°C for 90 minutes to thermally cure the sealant, and then allowed to cool at room temperature to create an empty cell. Liquid crystal (MLC-3022, manufactured by Merck) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to create a liquid crystal cell.

[0117] <Evaluation of Voltage Holding Ratio (VHR)> To evaluate the voltage holding ratio, a voltage of 1 V was applied to the obtained liquid crystal cell at a temperature of 60°C for 60 μs, and the voltage after 1667 ms was measured. The extent to which the voltage was held, i.e., the variation from the initial value, was calculated as the voltage holding ratio. The voltage holding ratio was measured using a voltage holding ratio measuring device VHR-1 manufactured by Toyo Corporation. The evaluation was performed by defining a VHR under the above conditions of 80% or more as "◯" and a VHR of less than 80% as "X".

[0118] The results of the migration resistance evaluation and the voltage holding ratio evaluation are shown in Table 2. All of the liquid crystal alignment films using the liquid crystal alignment agents shown in the Examples had good migration resistance evaluations. Furthermore, in Comparative Example 7, which used F-4, which is known as a rust inhibitor like B-1 and B-2 included in the scope of compound (B) of the present invention, as an additive, the voltage holding ratio was poor, but in Examples 2 and 8, which used B-1 and B-2, the voltage holding ratio was also good. Furthermore, even when B-2 was used, in Comparative Example 9, where the content of carboxy groups bonded to the aromatic ring was greater than 5 parts by mass, the migration resistance evaluation was poor.

[0119]

[0120] 1: Glass substrate 2: Silver 3: Liquid crystal alignment film 4: Conductive tape

[0121] The entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2022-23238 filed on February 17, 2022 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent comprising the following component (A) and a compound (B) represented by the following formula (1): Component (A): A polymer selected from the group consisting of polyimide precursors obtained by polymerizing a diamine component with a tetracarboxylic acid derivative component containing at least one compound selected from the group consisting of tetracarboxylic acid dianhydrides and derivatives thereof, and polyimides which are imidized products of the polyimide precursors, wherein the polymer (A) has a content of carboxy groups bonded to aromatic rings of 5 parts by mass or less per 100 parts by mass of the polymer. 【Chemistry 1】 (A １ represents a monovalent group having a trialkoxysilyl group or a hydrogen atom. ２ each independently represents an alkyl group having 1 to 4 carbon atoms, a carboxy group, or a hydrogen atom.

2. In the compound (B), A ２ The liquid crystal aligning agent according to claim 1 , wherein at least one of represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or a carboxy group.

3. In the compound (B), A １ The liquid crystal aligning agent according to claim 1, wherein is a monovalent group represented by "AX-*". (A represents a trialkoxysilyl group. X represents -(CH ２ ) ｎ -(n is an integer of 1 to 18), or the -(CH ２ ) ｎ -of-CH ２ - at least a part of - to -CONH-, -NHCO-, -CO-N(CH ３ ) represents a group in which X is replaced by any of -, -NH-, -O-, -COO-, or -OCO-. Any hydrogen atom possessed by X may be substituted by a halogen atom, a carboxy group, a hydroxy group, a cyano group, or a nitro group. * represents the bonding position.

4. The liquid crystal aligning agent according to claim 1, wherein the compound (B) is represented by any one of the following formulas (b-1) to (b-4): 【Chemistry 2】

5. In the component (A), the diamine component contains at least one diamine having a nitrogen atom-containing structure selected from the group consisting of a heterocyclic ring containing a nitrogen atom, a secondary or tertiary amino group. The liquid crystal aligning agent according to claim 1.

6. The liquid crystal aligning agent according to claim 1 , wherein in the component (A), the tetracarboxylic acid derivative component comprises a tetracarboxylic acid dianhydride represented by the following formula (2): 【Transformation 3】 (X represents a structure selected from the group consisting of the following formulae (x-1) to (x-17) and (xr-1) to (xr-2).) 【Chemistry 4】 (R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, or a phenyl group. ５ and R ６ each independently represents a hydrogen atom or a methyl group. *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group.

7. 2. The liquid crystal aligning agent according to claim 1, wherein the content of the compound (B) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A).

8. The liquid crystal alignment agent according to claim 1, further comprising an additive component selected from a crosslinking compound, an adhesion aid, a dielectric or conductive material for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film, a stabilizer, a surfactant, and an antifoaming agent.

9. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 8 to a substrate, baking the applied film, and irradiating the resulting film with polarized radiation.

10. A method for producing a liquid crystal alignment film, comprising applying the liquid crystal aligning agent according to any one of claims 1 to 8 to a substrate, baking the applied film, and subjecting the resulting film to a rubbing treatment.

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

12. 10. The method for producing a liquid crystal alignment film according to claim 9, wherein an electrode or wiring containing silver is disposed on the surface of the substrate to which the liquid crystal alignment agent is applied.

13. The method for producing a liquid crystal alignment film according to claim 10, wherein an electrode or wiring containing silver is disposed on the surface of the substrate to which the liquid crystal alignment agent is applied.

14. A liquid crystal display device comprising the liquid crystal alignment film according to claim 11.

15. 15. The liquid crystal display element according to claim 14, wherein a material containing silver is used for the electrodes and / or wiring of the liquid crystal display element.

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