Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and polymer and diamine used in liquid crystal display element

Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, a high-performance liquid crystal display element provided with the liquid crystal alignment film, and a polymer and a diamine used in the liquid crystal display element. The liquid crystal aligning agent widens the range of light irradiation amount for obtaining a liquid crystal aligning film with small deviation (non-uniformity) of the twisting angle of liquid crystal in a liquid crystal aligning film plane, and is used for obtaining a liquid crystal aligning film which does not generate display non-uniformity caused by a cleaning process and forming a liquid crystal aligning film with a high water contact angle. The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element provided with the liquid crystal alignment film. The present invention is characterized by containing at least one polymer (P) selected from the group consisting of polyimide precursors obtained using a diamine component containing a diamine (0) represented by formula (DA) and polyimides that are imides of the polyimide precursors. (The definition of each symbol is as defined in the description. > # imgabs0 #

Description

[0001] This application is a divisional application of the following application:

[0002] Title of the Invention: Liquid Crystal Alignment Agent, Liquid Crystal Alignment Film, and Liquid Crystal Display Element.

[0003] International Application Date: October 21, 2022.

[0004] International Application Number: PCT / JP2022 / 039295.

[0005] National Application Number: 202280030488.5. Technical Field

[0006] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. Background Art

[0007] Liquid crystal display elements are widely used in applications ranging from small-sized ones such as mobile phones and smartphones to larger-sized ones such as televisions and monitors. In addition, various driving methods different in electrode structure, physical properties of liquid crystal molecules used, etc. have been developed. For example, liquid crystal display elements using various modes such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, VA (Vertical Alignment) mode, IPS (In-Plane Switching) mode, and FFS (Fringe Field Switching) mode are known. These liquid crystal display elements generally have a liquid crystal alignment film that is indispensable for controlling the alignment state of liquid crystal molecules. As a material for the liquid crystal alignment film, polyamic acid and polyimide are usually used in consideration of various characteristics such as heat resistance, mechanical strength, and affinity with liquid crystal.

[0008] Currently, the most industrially popular liquid crystal alignment film is produced by performing a so-called rubbing alignment treatment, which is to rub the surface of a resin film such as polyimide formed on an electrode substrate unidirectionally with a cloth such as cotton, nylon, or polyester. The rubbing alignment treatment is a useful method that is simple and has excellent productivity. As an alignment treatment method alternative to the rubbing alignment treatment, a photoalignment treatment method of imparting liquid crystal alignment ability by irradiating polarized radiation is known. Regarding the photoalignment treatment method, methods using a photoisomerization reaction, a photocrosslinking reaction, a photodecomposition reaction, etc. have been proposed (for example, refer to Non-Patent Document 1, Patent Document 1, and Patent Document 2).

[0009] Prior Art Documents

[0010] Patent document

[0011] Patent document 1: Japanese Patent Laid-Open No. 9-297313

[0012] Patent document 2: Japanese Patent Laid-Open No. 2004-206091

[0013] Non-patent document

[0014] Non-patent document 1: "Liquid Crystal Photoalignment Film", Functional Materials, November 1997, Vol. 17, No. 11, pp. 13-22 Summary of the invention

[0015] Problems to be solved by the invention

[0016] In recent years, with the high-performance of liquid crystal display elements, in addition to large-screen and high-definition liquid crystal TVs, etc., applications to in-vehicle use, such as monitors for car navigation systems, instrument panels, surveillance cameras, and medical cameras, have also been studied. Therefore, the requirements for high-performance, especially high-definition, of liquid crystal display elements have been further increased. As a liquid crystal alignment film, a liquid crystal alignment film that can further improve various characteristics of liquid crystal display elements is required.

[0017] In addition, with the increase in the size of liquid crystal display elements, an adverse situation occurs in which the twist angle of the liquid crystal in the plane of the liquid crystal display element is slightly uneven due to deviations in the manufacturing process. Such deviations cause uneven brightness in the plane when the liquid crystal display element is set to black display, reducing the quality of the liquid crystal display element.

[0018] Moreover, in the above-mentioned rubbing alignment treatment and photoalignment treatment, in order to remove impurities, a cleaning process using a solvent is sometimes performed after the above-mentioned alignment treatment. In this cleaning process, beads of the solvent are formed, droplets are generated during air knife drying, etc., and the film surface is unevenly cleaned locally. In the obtained liquid crystal display element, linear display unevenness along the air knife direction sometimes occurs.

[0019] The present invention has been completed in view of the above circumstances, and its object is to provide a liquid crystal aligning agent that expands the range of the light irradiation amount of a liquid crystal alignment film that can obtain a small deviation (non-uniformity) in the twist angle of the liquid crystal in the plane of the liquid crystal alignment film, and that can be used to obtain a liquid crystal alignment film that does not cause display unevenness due to the cleaning process and can form a liquid crystal alignment film having a high water contact angle, and a liquid crystal display element including the liquid crystal alignment film.

[0020] Solutions to solve the problems

[0021] The inventors of the present invention conducted in-depth research to solve the above technical problems and found that a liquid crystal aligning agent containing a polymer using a diamine having a specific structure is effective for achieving the above object, thus completing the present invention.

[0022] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film. The liquid crystal aligning agent is characterized by containing at least one polymer (P) selected from the group consisting of a polyimide precursor obtained from a diamine component using a diamine (0) represented by the following formula (D A ) and a polyimide which is an imidized product of the polyimide precursor.

[0023]

[0024] (Ar represents any divalent aromatic group among a divalent benzene ring, a biphenyl structure, or a naphthalene ring, and any hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring is optionally substituted with a monovalent group. m and n are each independently an integer of 1 to 3.

[0025] Any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded is optionally substituted with a monovalent group.)

[0026] It should be noted that in the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Boc represents a tert-butoxycarbonyl group.

[0027] Advantages of the Invention

[0028] According to the present invention, a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, and a high-performance liquid crystal display element having the liquid crystal alignment film can be obtained. The liquid crystal aligning agent expands the range of light irradiation amounts of a liquid crystal alignment film in which the deviation (non-uniformity) of the twist angle of liquid crystals in the plane of the liquid crystal alignment film is small, and is used to obtain a liquid crystal alignment film that does not cause display unevenness due to a cleaning process and to form a liquid crystal alignment film having a high water contact angle.

[0029] The mechanism for obtaining the above effects of the present invention is not necessarily clear, but is roughly presumed as follows. It is considered that a liquid crystal alignment film with a small deviation in the twist angle of liquid crystals is obtained through the oxyaniline structure contained in the diamine (0) of the present invention, and the water contact angle is increased by the introduction of hydrophobic hydrocarbons such as aromatic rings and alkylene groups, thus obtaining the above effects. Detailed Description of the Invention

[0030] <Specific Diamine>

[0031] As described above, the liquid crystal aligning agent of the present invention is characterized by containing at least one selected from the group consisting of a polyimide precursor obtained from a diamine component using a diamine represented by the following formula (D AAt least one polymer (P) selected from the group consisting of a polyimide precursor obtained from the diamine component of the diamine (0) (also referred to as a specific diamine in the present invention) and a polyimide which is an imidized product of the polyimide precursor.

[0032]

[0033] In the above formula (D A ), Ar, m, and n are each as defined above.

[0034] In the above formula (D A ), from the viewpoint of obtaining high liquid crystal orientation, m and n are preferably 1 to 2.

[0035] Examples of the monovalent group that replaces the hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring of Ar in the above formula (D A ) include: a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, a carboxyl group, a hydroxyl group, an alkyloxycarbonyl group having 1 to 3 carbon atoms, a cyano group, a nitro group, etc. Among them, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a fluoroalkoxy group having 1 to 3 carbon atoms is preferred.

[0036] In addition, any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded may be optionally substituted with a monovalent group. Specific examples of the monovalent group include the monovalent groups exemplified for Ar in the above formula (D A ), and as a preferred embodiment, the same monovalent groups can be cited.

[0037] Suitable examples of the divalent aromatic group represented by Ar include: 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, biphenyl-4,4'-diyl, 2-methylbiphenyl-4,4'-diyl, 2-ethylbiphenyl-4,4'-diyl, 2-propylbiphenyl-4,4'-diyl, 2-methoxybiphenyl-4,4'-diyl, 2-ethoxybiphenyl-4,4'-diyl, 2-fluorobiphenyl-4,4'-diyl, 3-methylbiphenyl-4,4'-diyl, 3-ethylbiphenyl-4,4'-diyl, 3-propylbiphenyl-4,4'-diyl, 3-methoxybiphenyl-4,4'-diyl, 3-ethoxybiphenyl-4,4'-diyl, 3-fluorobiphenyl-4,4'-diyl, 2,2'-dimethylbiphenyl-4,4'-diyl, 3,3'-dimethylbiphenyl-4,4'-diyl, biphenyl-3,3'-diyl, 5-methylbiphenyl-3,3'-diyl, 5,5'-dimethylbiphenyl-3,3'-diyl, 1,5-naphthylene, 2,6-naphthylene, or 1-methyl-2,6-naphthylene, etc.

[0038] As a preferred example of the above formula (D A ), the following formulas (d A -1) to (d A -3) can be cited. In the following formulas (d A -1) to (d A -3), any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded, the benzene ring bonded to the alkylene group, the biphenyl structure, or the naphthalene ring is optionally substituted with a monovalent group. Specific examples of the monovalent group include the monovalent groups exemplified by Ar in the above formula (D A ), and the same monovalent groups can be cited as a preferred embodiment. As the above formulas (d A -1) to (d AThe substituent of the hydrogen atom on the benzene ring bonded to the amino groups at both ends in (0) - 3) is more preferably a methyl group, which is a monovalent group. In addition, when the hydrogen atoms on the benzene ring bonded to the amino groups at both ends are substituted, in each benzene ring, it is more preferable that 1 to 2 hydrogen atoms are substituted, and further preferably 1 hydrogen atom is substituted. At least one hydrogen atom on the benzene ring bonded to the amino groups at both ends is optionally substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a fluoroalkoxy group having 1 to 3 carbon atoms.

[0039]

[0040] (m and n each independently have the above definitions.)

[0041] (Polymer (P))

[0042] The polymer (P) contained in the liquid crystal aligning agent of the present invention is a polyimide precursor obtained by using a diamine component containing the above diamine (0), or a polyimide which is an imidized product of the polyimide precursor. Here, the polyimide precursor is a polymer that can obtain a polyimide through imidization of polyamic acid, polyamic acid ester, etc. The polymer (P) can be used alone or in combination of two or more.

[0043] The above polymer (P) can be a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1).

[0044]

[0045] (In formula (1), X1 represents a tetravalent organic group. Y1 is a divalent organic group obtained by removing two amino groups from the above specific diamine. R and Z each independently represent a hydrogen atom or a monovalent organic group.)

[0046] Examples of the monovalent organic group for R and Z in the above formula (1) include: a monovalent hydrocarbon group having 1 to 6 carbon atoms, -O-, -S-, -CO-, -COO-, -COS-, -NR 3 -, -CO-NR 3 -, -Si(R 3 )2 - (wherein, R 3a monovalent group A in which the methylene group of the hydrocarbon group is substituted by a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms), -SO2-, etc., and a monovalent group obtained by substituting at least one hydrogen atom bonded to a carbon atom of the above monovalent hydrocarbon group or the above monovalent group A with a halogen atom, a hydroxyl 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 carboxyl group, a cyano group, a sulfo group, an acyl group, etc., and a monovalent group having a heterocycle.

[0047] As the monovalent organic group in R and Z in the above formula (1), among them, 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, or a tert-butoxycarbonyl group is preferred, and an alkyl group having 1 to 3 carbon atoms is further preferred, and a methyl group is even more preferred.

[0048] From the viewpoint of appropriately obtaining 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.

[0049] As X1 in the above formula (1), for example, a tetravalent organic group derived from a tetracarboxylic dianhydride or its derivative described later can be mentioned. As a preferred embodiment of the tetracarboxylic dianhydride or its derivative in the above X1, a preferred embodiment of the tetracarboxylic dianhydride or its derivative that can be used for the synthesis of the polymer (P) described later can be mentioned.

[0050] The polyamic acid (P') as the polyimide precursor of the above polymer (P) can be obtained by a polymerization reaction of a diamine component containing the above diamine (0) and a tetracarboxylic acid component. The above diamine (0) can be used alone or in combination of two or more.

[0051] The usage amount of the diamine (0) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more based on the total diamine component.

[0052] The diamine component used for the production of the above polyamic acid (P') may also contain a diamine other than the diamine (0) (hereinafter also referred to as other diamines). When other diamines are used in addition to the above diamine (0), the usage amount of the diamine (0) based on the diamine component is preferably 90 mol% or less, and more preferably 80 mol% or less.

[0053] Examples of other diamines are listed below, but are not limited thereto. The above-mentioned other diamines may be used alone or in combination of two or more. p-Phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, the following formula (d AL -1) to (d ALThe diamines shown in (-10), 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, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 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 (hereinafter these diamines will also be referred to as other diamines (a)); diamines having a photo-orienting group such as 4,4'-diaminoazobenzene or diaminodiphenylacetylene; diamines having a photopolymerizable group at the end such as 2-(2,4-diaminophenoxy)ethyl methacrylate or 2,4-diamino-N,N-diallylaniline; diamines having a function of a radical polymerization initiator such as 1-(4-(2-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylpropanone or 2-(4-(2-hydroxy-2-methylpropanoyl)phenoxy)ethyl 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, 1,3-bis(4-aminobenzyl)urea, 1,3-bis(4-aminophenethyl)urea;3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2,2-bis(3-amino-4-methylphenyl)propane, 4,4'-diaminobenzophenone, 1,4-bis(4-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-oxazoline]-aniline, or a heterocyclic diamine such as a diamine represented by the following formula (z-1) to formula (z-13), or 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, etc., a diamine having a diphenylamine structure and 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 (hereinafter also referred to as a specific nitrogen atom-containing structure) (wherein, the molecule does not have an amino group bonded to a protecting group that dissociates by heating and is replaced by a hydrogen atom); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diamino-3,3'-dihydroxybiphenyl;Diamines having a carboxyl 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, 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid; 4-(2-(methylamino)ethyl)aniline, 4-(2-aminoethyl)aniline, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine; diamines having a group "-N(D)-" (where D represents a protecting group that is removed by heating and replaced with a hydrogen atom, preferably a carbamate protecting group, more preferably a tert-butoxycarbonyl group) such as those represented by the following formulas (5-1) to (5-6), cholesteryloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanosterol 3,5-diaminobenzoate, and 3,6-bis(4-aminobenzoyloxy)cholestane, etc., diamines having a steroid skeleton; diamines represented by the following formulas (V-1) to (V-2); diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane; m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), diamines having two amino groups bonded to any one of the groups represented by the formulas (Y-1) to (Y-167) described in International Publication No. 2018 / 117239, etc.;

[0054]

[0055] (In formulas (d AL -6) and (d AL -8), m1 and m2 each independently have the above definitions.)

[0056]

[0057]

[0058] In the above formula (V-1), m and n are each independently an integer of 0 to 3, satisfying 1 ≤ m + n ≤ 4. j is an integer of 0 or 1. X 1 represents -(CH2) a -(where a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. R 1 represents a fluorine atom, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a monovalent group such as an alkoxyalkyl group having 2 to 10 carbon atoms. In the above formula (V-2), X 2 represents -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-. When there are two m, n, X 1 , R 1 , they each independently have the above definitions.

[0059] Regarding the diamine component used for the production of the above polyamic acid (P'), from the viewpoint of appropriately obtaining the effects of the present invention, preferably, it contains at least one diamine selected from the group consisting of the above other diamines (a).

[0060] When using other diamines in addition to the above diamine (0), the usage amount of the above other diamines is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on all the diamine components used for the production of the polymer (P).

[0061] (Tetracarboxylic acid component)

[0062] When producing the above polyamic acid (P'), as the tetracarboxylic acid component that reacts with the diamine component, not only tetracarboxylic dianhydrides but also derivatives of tetracarboxylic dianhydrides such as tetracarboxylic acids, tetracarboxylic dihalides, tetraalkyl esters of tetracarboxylic acids, or tetraalkyl ester dihalides of tetracarboxylic acids can be used.

[0063] Examples of the above tetracarboxylic dianhydride or its derivative include acyclic aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, or their derivatives. Among them, more preferably, it contains a tetracarboxylic dianhydride or its derivative having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. In particular, further preferably, it contains a tetracarboxylic dianhydride or its derivative having at least one structure selected from the group consisting of a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

[0064] The above tetracarboxylic dianhydride or its derivative can be used alone or in combination of two or more.

[0065] It should be noted that the non-cyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. Among them, it does not need to be composed only of a chain hydrocarbon structure, and it may also have an alicyclic structure or an aromatic ring structure in a part thereof.

[0066] The alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Among them, none of these four carboxyl groups are bonded to an aromatic ring. In addition, it does not need to be composed only of an alicyclic structure, and it may also have a chain hydrocarbon structure or an aromatic ring structure in a part thereof.

[0067] The aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. Among them, it does not need to be composed only of an aromatic ring structure, and it may also have a chain hydrocarbon structure or an alicyclic structure in a part thereof.

[0068] As the tetracarboxylic acid component that can be used for the production of the above polyamic acid (P'), it is preferably to include the following tetracarboxylic dianhydride or its derivative (in the present invention, they are also collectively referred to as specific tetracarboxylic acid derivatives).

[0069] Acyclic aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 4-(2,5-dioxotetrahydrofuran-3-yl)tetralin-1,2-dicarboxylic anhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride; aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)-2,2-diphenylpropane dianhydride, ethylene glycol bisanhydrotrimellitate, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-carbonyldiphthalic anhydride, 4,4'-(1,4-phenylenedioxy)bis(phthalic anhydride), or 4,4'-methylenebis(1,4-phenylenedimethylene)bis(phthalic anhydride); and tetracarboxylic dianhydrides such as those described in JP-A-2010-97188.

[0070] As preferred examples of the above-mentioned specific tetracarboxylic acid derivatives, there are 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, or their derivatives.

[0071] The usage ratio of the above-mentioned specific tetracarboxylic acid derivatives is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 50 mol% or more, based on all the tetracarboxylic acid components used.

[0072] (Liquid crystal aligning agent)

[0073] The liquid crystal aligning agent of the present invention is a liquid composition in which a polymer (P) and other components used as required are preferably dispersed or dissolved in a suitable solvent.

[0074] The total content of the polymer components contained in the liquid crystal aligning agent of the present invention can also be appropriately changed according to the setting of the thickness of the coating film to be formed. However, from the aspect of forming a uniform and defect-free coating film, it is preferably 1 mass% or more based on the total mass of the liquid crystal aligning agent, and preferably 10 mass% or less from the aspect of the storage stability of the solution.

[0075] The content of the polymer (P) used in the present invention is preferably 1 to 100 parts by mass, more preferably 10 to 100 parts by mass, and particularly preferably 20 to 100 parts by mass, based on 100 parts by mass in total of the polymers contained in the liquid crystal aligning agent.

[0076] The liquid crystal aligning agent of the present invention may contain other polymers in addition to the polymer (P). When specific examples of other polymers are listed, polymers selected from the group consisting of, for example, polymers selected from the group consisting of polyimide precursors obtained by using diamine components not containing the above specific diamine and polyimides which are imidized products of the polyimide precursors (also referred to as polymer (B) in the present invention), polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene - maleic anhydride) copolymers, poly(isobutylene - maleic anhydride) copolymers, poly(vinyl ether - maleic anhydride) copolymers, poly(styrene - phenylmaleimide) derivatives, and poly(meth)acrylates can be listed.

[0077] Specific examples of the poly(styrene - maleic anhydride) copolymer include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing), etc. Specific examples of the poly(isobutylene - maleic anhydride) copolymer include ISOBAM - 600 (manufactured by Kuraray). Specific examples of the poly(vinyl ether - maleic anhydride) copolymer include Gantrez AN - 139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland).

[0078] Among them, from the aspect of reducing the afterimage derived from residual DC, polymer (B) is more preferred.

[0079] The above other polymers may be used alone, or two or more of them may be used in combination. The content ratio of the other polymers is preferably 90 parts by mass or less, more preferably 10 - 90 parts by mass, and further preferably 20 - 80 parts by mass with respect to 100 parts by mass in total of the polymers contained in the liquid crystal aligning agent.

[0080] The content of the above polymer (P) may be 90 parts by mass or less, or may be 80 parts by mass or less with respect to 100 parts by mass in total of the polymers contained in the liquid crystal aligning agent.

[0081] (polymer (B))

[0082] Regarding specific examples of the tetracarboxylic acid component for the production of the above-mentioned polymer (B), compounds similar to those exemplified for the polymer (P) can be cited, including preferred specific examples. More preferably, the tetracarboxylic acid component for the production of the polymer (B) more preferably contains a tetracarboxylic dianhydride or a derivative thereof having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring, still more preferably the above-mentioned specific tetracarboxylic acid derivative, and most preferably a more preferred specific example of the above-mentioned specific tetracarboxylic acid derivative.

[0083] In addition, the usage amount of the above-mentioned specific tetracarboxylic acid derivative is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 50 mol% or more, based on all the tetracarboxylic acid components used for the production of the polymer (B).

[0084] Examples of the diamine component for obtaining the polymer (B) include the diamines exemplified for the above-mentioned polymer (P). Among them, preferred are diamines containing at least one group selected from the group consisting of a urea bond, an amide bond, a carboxyl group, and a hydroxyl group in the molecule, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, the diamines represented by the above formulas (d AL -1) to (d AL -10), and the diamines having the above-mentioned specific nitrogen atom-containing structure (also referred to as specific diamine (b) in the present invention). The above diamine component may be used alone or in combination of two or more.

[0085] When using the above-mentioned specific diamine (b), its usage amount is preferably 10 mol% or more, more preferably 20 mol% or more, based on all the diamine components used for the production of the polymer (B). When using a diamine other than the specific diamine (b), its usage amount is preferably 90 mol% or less, more preferably 80 mol% or less, based on all the diamine components used for the production of the polymer (B).

[0086] (Production of polyamic acid)

[0087] The production of polyamic acid is carried out by reacting a diamine component with a tetracarboxylic acid component in an organic solvent. The usage ratio of the tetracarboxylic acid component to the diamine component for the production reaction of polyamic acid preferably corresponds to a ratio of 0.5 to 2 equivalents of the acid anhydride group of the tetracarboxylic acid component per 1 equivalent of the amino group of the diamine component, and still more preferably, the acid anhydride group of the tetracarboxylic acid component is 0.8 to 1.2 equivalents per 1 equivalent of the amino group of the diamine component. Similar to a usual polycondensation reaction, the closer the equivalent of the acid anhydride group of the tetracarboxylic acid component is to 1 equivalent, the larger the molecular weight of the resulting polyamic acid.

[0088] The reaction temperature in the production of polyamic acid is preferably -20 to 150 °C, more preferably 0 to 100 °C. In addition, the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The production of polyamic acid can be carried out at any concentration. The concentration of polyamic acid is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. It is carried out at a high concentration in the initial stage of the reaction, and then a solvent can be added.

[0089] Specific examples of the above organic solvents include: cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone. In addition, when the solvent solubility of the polymer is high, solvents such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 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.

[0090] (Production of polyamic acid ester)

[0091] Polyamic acid ester can be obtained, for example, by known methods such as the following: [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

[0092] (Production of polyimide)

[0093] Regarding polyimide, polyimide can be obtained by subjecting a polyimide precursor such as the above polyamic acid or polyamic acid ester to ring closure (imidization). It should be noted that the imidization rate mentioned in this specification refers to the proportion of the imide group in the total amount of the imide group and the carboxyl group (or its derivative) derived from the tetracarboxylic dianhydride or its derivative. The imidization rate does not necessarily have to be 100%, and it can be arbitrarily adjusted according to the use and purpose.

[0094] As a method for imidizing the polyimide precursor, thermal imidization in which the solution of the polyimide precursor is directly heated or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor can be cited.

[0095] When carrying out thermal imidization of the polyimide precursor in solution, the temperature is preferably 100 to 400 °C, more preferably 120 to 250 °C, and it is preferably carried out while removing the water generated by the imidization reaction out of the system.

[0096] The catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, preferably with stirring at -20 to 250 °C, more preferably at 0 to 180 °C. The amount of the basic catalyst is preferably 0.5 to 30 molar times, more preferably 2 to 20 molar times, of the amic acid group, and the amount of the acid anhydride is preferably 1 to 50 molar times, more preferably 3 to 30 molar times, of the amic acid group. As the basic catalyst, pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. can be cited. Among them, pyridine has a moderate basicity for the reaction to proceed, so it is preferred. As the acid anhydride, acetic anhydride, trimellitic anhydride, pyromellitic dianhydride, etc. can be cited. Among them, if acetic anhydride is used, the purification after the reaction is completed becomes easy, so it is preferred. The imidization rate based on catalytic imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

[0097] When recovering the produced polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, it is only necessary to pour the reaction solution into a solvent and precipitate it. As the solvent for precipitation, methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, etc. can be cited. After the polymer poured into the solvent and precipitated is filtered and recovered, it can be dried at normal pressure or reduced pressure, at room temperature or by heating. In addition, when the recovered polymer is repeatedly subjected to the operations of redissolving with an organic solvent, reprecipitating, and recovering 2 to 10 times, the impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, or hydrocarbons can be cited. If three or more solvents selected from these are used, the purification efficiency is further improved, so it is preferred.

[0098] When manufacturing the polyimide precursor and polyimide in the present invention, an appropriate end-capping agent can also be used together with the tetracarboxylic acid component containing a tetracarboxylic dianhydride or its derivative and the diamine component containing the above diamine to manufacture an end-capped polymer. The end-capped polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by coating and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.

[0099] As examples of the ends of the polyimide precursor and polyimide in the present invention, amino group, carboxyl group, acid anhydride group, or a group derived from an end-capping agent described later can be cited. The amino group, carboxyl group, and acid anhydride group can be obtained by ordinary condensation reactions or by end-capping using the following end-capping agents.

[0100] Examples of the capping agent include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilylpropyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate, diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, nicotinoyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine; isocyanates having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc.

[0101] The usage ratio of the capping agent is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, relative to 100 mol parts in total of the diamine components used.

[0102] The polystyrene-reduced weight-average molecular weight (Mw) of the polyimide precursor and the polyimide measured by gel permeation chromatography (GPC) is preferably 1000 to 500000, more preferably 2000 to 300000. In addition, the molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-reduced number-average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less. By being within this molecular weight range, good liquid crystal alignment properties of the liquid crystal display element can be ensured.

[0103] The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as it can uniformly dissolve the polymer (P) and other polymers added as needed. For example, the following can be cited: 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,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-(3-methoxypropyl)-2-pyrrolidone, N-(2-ethoxyethyl)-2-pyrrolidone, N-(4-methoxybutyl)-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively referred to as good solvents), etc. Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide or γ-butyrolactone is 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.

[0104] In addition, the organic solvent contained in the liquid crystal aligning agent preferably uses a mixed solvent in which, in addition to the above solvents, a solvent (also called a poor solvent) that improves the coatability and the surface smoothness of the coating film when coating the liquid crystal aligning agent is used in combination. Specific examples of the poor solvent are described below, but are not limited thereto. 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 according to the coating device, coating conditions, coating environment, etc. of the liquid crystal aligning agent.

[0105] Examples of the poor solvent include diisopropyl ether, diisobutyl ether, 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 ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, amyl 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 monomethyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxyethoxy)-1-propanol, propylene glycol monomethyl ether acetate, 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, 2,6-dimethyl-4-heptanone, etc.

[0106] Among them, 2,6-dimethyl-4-heptanol, 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 2,6-dimethyl-4-heptanone are preferred.

[0107] Examples of preferred combinations of solvents as good solvents and poor solvents include: N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and ethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether; N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-ethyl-2-pyrrolidone and propylene glycol diacetate; N,N-dimethyl lactamide and diisobutyl ketone; N-methyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-ethyl-2-pyrrolidone and ethyl 3-ethoxypropionate; N-methyl-2-pyrrolidone, ethyl 3-ethoxypropionate, and dipropylene glycol monomethyl ether; 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, diethylene glycol monomethyl ether, and butyl cellosolve acetate; N,N-dimethyl lactamide and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-ethyl-2-pyrrolidone and N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone, N-ethyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and 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 and 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone, γ-butyrolactone and 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl ketone, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone and γ-butyrolactone and propylene glycol monobutyl ether and diisobutyl carbinol, N-methyl-2-pyrrolidone and γ-butyrolactone and dipropylene glycol dimethyl ether, N-methyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and diethylene glycol diethyl ether and dipropylene glycol monomethyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and propylene glycol diacetate, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether and diisobutyl ketone, N-ethyl-2-pyrrolidone and γ-butyrolactone and diisobutyl ketone, N-ethyl-2-pyrrolidone and N,N-dimethyl lactamide and diisobutyl ketone, N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate, γ-butyrolactone and ethylene glycol monobutyl ether acetate and dipropylene glycol dimethyl ether, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether acetate and propylene glycol dimethyl ether, N-methyl-2-pyrrolidone and 4-methyl-2-pentyl acetate and ethylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and cyclohexyl acetate and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and propylene glycol monomethyl ether, cyclopentanone and propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and cyclohexanone and propylene glycol monomethyl ether, etc.

[0108] (Liquid crystal aligning agent)

[0109] In addition to the above-mentioned polymer (P), the above-mentioned other polymers, and the above-mentioned organic solvents, the liquid crystal aligning agent of the present invention may further contain components other than these (hereinafter also referred to as additive components). Examples of the above-mentioned additive components include at least one crosslinking compound selected from the group consisting of crosslinking compounds having at least one substituent selected from the group consisting of oxiranyl group, oxetanyl group, blocked isocyanate group, oxazolinyl group, cyclic carbonate group, hydroxyl group, and alkoxy group, and crosslinking compounds having a polymerizable unsaturated group; functional silane compounds; metal chelate compounds; curing accelerators; surfactants; antioxidants; sensitizers; preservatives; compounds for adjusting the dielectric constant and resistance of the obtained liquid crystal alignment film, and the like.

[0110] As preferred specific examples of the above crosslinkable compounds, the following can be cited: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6 - hexanediol diglycidyl ether, glycerol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 - tetraglycidyl - 2,4 - hexanediol, bisphenol A type epoxy resins such as EPIKOTE 828 (manufactured by MITSUBISHI CHEMICAL), bisphenol F type epoxy resins such as EPIKOTE 807 (manufactured by MITSUBISHI CHEMICAL), hydrogenated bisphenol A type epoxy resins such as YX - 8000 (manufactured by MITSUBISHI CHEMICAL), epoxy resins containing a biphenyl skeleton such as YX6954BH30 (manufactured by MITSUBISHI CHEMICAL), phenol novolac type epoxy resins such as EPPN - 201 (manufactured by Nippon Kayaku Co., Ltd.), (ortho, meta, para) cresol novolac type epoxy resins such as EOCN - 102S (manufactured by Nippon Kayaku Co., Ltd.), isocyanuric acid triglycidyl esters such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), alicyclic epoxy resins such as CELOXIDE 2021P (manufactured by Daicel Chemical Industries, Ltd.), compounds containing a tertiary nitrogen atom represented by N,N,N',N' - tetraglycidyl - m - xylylenediamine, 1,3 - bis(N,N - diglycidylaminomethyl) cyclohexane, or N,N,N',N' - tetraglycidyl - 4,4' - diaminodiphenylmethane; compounds having two or more oxirane groups such as tetrakis(glycidyloxymethyl) methane; compounds having two or more oxetanyl groups described in paragraphs 0170 to 0175 of WO2011 / 132751; compounds having a blocked isocyanate group such as CORONATE APstable M, CORONATE 2503, 2515, 2507, 2513, 2555, MILLIONATE MS - 50 (the above are manufactured by TOSOH Corporation), TAKENATE B - 830, B - 815N, B - 820NSU, B - 842N, B - 846N, B - 870N, B - 874N, B - 882N (the above are manufactured by Mitsui Chemicals, Inc.); compounds having an oxazoline 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 - tri - (2 - oxazolinyl - 2) - benzene, EPOCROS (manufactured by NIPPON SHOKUBAI); compounds having a cyclic carbonate group described in paragraphs 0025 to 0030, 0032 of WO2011 / 155577;Compounds having hydroxyl groups and alkoxy groups, such as N,N,N',N'-tetrakis(2-hydroxyethyl)adipamide, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethoxymethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)-1,1,1,3,3,3-hexafluoropropane; compounds represented by glycerol mono(meth)acrylate, glycerol di(meth)acrylate (mixture of 1,2- and 1,3-types), glycerol tri(meth)acrylate, glycerol 1,3-diglycolate 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.;

[0111] The content of the above crosslinkable compound 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.

[0112] As the compound for adjusting the dielectric constant and resistance, a monoamine having an aromatic heterocycle containing a nitrogen atom, such as 3-aminomethylpyridine, can be cited. The content of the monoamine having an aromatic heterocycle containing a nitrogen atom 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.

[0113] As preferred specific examples of the above functional silane compounds, the following can be cited: 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-ethoxycyclohexyl)ethyltrimethoxysilane, 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, relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.

[0114] The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent in the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 to 10% by mass.

[0115] The particularly preferred range of the solid content concentration varies depending on the method used when coating the liquid crystal aligning agent on the substrate. For example, in the case of using the spin coating method, the solid content concentration is particularly preferably 1.5 to 4.5% by mass. In the case of using the printing method, it is particularly preferred to set the solid content concentration to 3 to 9% by mass, thereby setting the solution viscosity to 12 to 50 mPa·s. In the case of using the inkjet method, it is particularly preferred to set the solid content concentration to 1 to 5% by mass, thereby setting the solution viscosity to 3 to 15 mPa·s. The temperature during the preparation of the liquid crystal aligning agent is preferably 10 to 50°C, more preferably 20 to 30°C.

[0116] (Liquid Crystal Alignment Film and Liquid Crystal Display Element)

[0117] The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the above liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, and for example, it can be applied to various operation modes such as TN (Twisted Nematic) mode, STN (Super Twisted Nematic) mode, vertical alignment mode (including VA (Vertical Alignment) - MVA (Multi - domain Vertical Alignment) mode, VA - PVA (Patterned Vertical Alignment) mode, etc.), in - plane switching mode (IPS (In - Plane Switching) mode, FFS (Fringe Field Switching) mode), optically compensated bend mode (OCB: Optically Compensated Bend mode), etc.

[0118] The liquid crystal display element of the present invention can be manufactured, for example, by 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).

[0119] <Step (1): Step of coating a liquid crystal aligning agent on a substrate>

[0120] Step (1) is a step of coating a liquid crystal aligning agent on a substrate. Specific examples of step (1) are described below.

[0121] The liquid crystal aligning agent is coated on one surface of a substrate provided with a patterned transparent conductive film by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, an inkjet method, or a spraying method. Here, as the material of the substrate, as long as it is a substrate with high transparency, there is no particular limitation, and plastics such as acrylic and polycarbonate can also be used together with glass and silicon nitride. In addition, in a reflective liquid crystal display element, if it is only a single - side substrate, an opaque material such as a silicon wafer can also be used, and in this case, a light - reflecting material such as aluminum can be used for the electrode. In addition, when manufacturing a liquid crystal display element of the IPS mode or the FFS mode, a substrate provided with an electrode composed of a transparent conductive film or a metal film patterned in a comb - tooth shape and a counter substrate not provided with an electrode are used.

[0122] An IPS substrate, which is a comb-shaped electrode substrate used in a liquid crystal display element of the IPS mode, for example, has: a substrate; a plurality of linear electrodes formed on the substrate and arranged in a comb shape; and a liquid crystal alignment film formed on the substrate so as to cover the linear electrodes.

[0123] It should be noted that an FFS substrate, which is a comb-shaped electrode substrate used in a liquid crystal display element of the FFS mode, for example, has: a substrate; a planar electrode formed on the substrate; an insulating film formed on the planar electrode; a plurality of linear electrodes formed on the insulating film and arranged in a comb shape; and a liquid crystal alignment film formed on the insulating film so as to cover the linear electrodes.

[0124] As a more preferable example of a method for coating a liquid crystal aligning agent on a substrate to form a film, there can be mentioned: printing methods such as screen printing, offset printing, or flexographic printing, spin coating method, inkjet method, or spraying method, etc. Among them, a coating and film-forming method by flexographic printing, spin coating method, or inkjet method can be appropriately used.

[0125] <Process (2): Process of firing the coated liquid crystal aligning agent>

[0126] Process (2) is a process of firing the liquid crystal aligning agent coated on the substrate to form a film. Specific examples of Process (2) are described below.

[0127] After coating the liquid crystal aligning agent on the substrate in Process (1), a heating unit such as a hot plate, a thermal cycle type oven, or an IR (infrared) type oven can be used to evaporate the solvent or perform thermal imidization of a polyimide precursor represented by polyamic acid. The drying and firing processes after coating the liquid crystal aligning agent can be carried out at any temperature and time, and can also be carried out multiple times. As the temperature for firing the liquid crystal aligning agent, for example, it can be carried out at 40 to 180 °C. From the viewpoint of shortening the process, it can be carried out at 40 to 150 °C. As the firing time, there is no particular limitation, and 1 to 10 minutes or 1 to 5 minutes can be mentioned. In the case of performing thermal imidization of a polyimide precursor represented by polyamic acid, after the above process, for example, a firing process at 150 to 300 °C or 150 to 250 °C can also be added. As the firing time, there is no particular limitation, and for example, 5 to 40 minutes, preferably 5 to 30 minutes of firing time can be mentioned.

[0128] If the film thickness of the fired film-like material is too thin, the reliability of the liquid crystal display element may sometimes decrease, so it is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0129] <Process (3): Process of performing an alignment treatment on the film obtained in Process (2)>

[0130] Step (3) is a step of subjecting the film obtained in step (2) to an alignment treatment as appropriate. That is, in a liquid crystal display element using a horizontal alignment method such as the IPS method or the FFS method, an alignment ability imparting treatment is performed on the coated film. On the other hand, in a liquid crystal display element using a vertical alignment method such as the VA method or the PSA (Polymer Sustained Alignment) method, the formed coated film can be directly used as a liquid crystal alignment film, but an alignment ability imparting treatment can also be performed on the coated film. As a method for aligning a liquid crystal alignment film, a rubbing alignment treatment method and a photoalignment treatment method can be cited. As a photoalignment treatment method, the following method can be cited: irradiating the surface of the above-mentioned film-like material with radiation polarized in a fixed direction, and performing a heat treatment as appropriate to impart liquid crystal alignment properties (also referred to as liquid crystal alignment ability). As the radiation, ultraviolet rays or visible light having a wavelength of 100 to 800 nm can be used. Among them, ultraviolet rays having a wavelength of 100 to 400 nm are preferred, and ultraviolet rays having a wavelength of 200 to 400 nm are more preferred.

[0131] The irradiation amount of the above-mentioned radiation is preferably 1 to 10,000 mJ / cm 2 , and among them, 100 to 5,000 mJ / cm is more preferred. 2 .

[0132] In addition, in the case of irradiating radiation, in order to improve the liquid crystal alignment properties, the substrate having the above-mentioned film-like material can be irradiated with radiation while being heated at 50 to 250 °C. The liquid crystal alignment film produced as described above can make liquid crystal molecules stably align in a fixed direction.

[0133] Moreover, in the above method, water or a solvent can also be used to perform a contact treatment on the coated film irradiated with polarized radiation or the coated film subjected to a rubbing alignment treatment. In addition, the film subjected to the above alignment treatment can be heat-treated without performing a contact treatment. Moreover, the film subjected to the above contact treatment can be further heat-treated.

[0134] The solvent used in the above contact treatment is not particularly limited as long as it is a solvent that dissolves the decomposition products generated from the film-like material due to the irradiation of radiation. As specific examples, water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, cyclohexyl acetate, etc. can be cited. The solvent can be one kind or a combination of two or more kinds.

[0135] The temperature for heat-treating the above-mentioned radiation-irradiated coating film is more preferably 50 to 300 °C, and further preferably 120 to 250 °C. As the time for heat treatment, each is preferably set to 1 to 30 minutes.

[0136] <Process (4): Process of manufacturing a liquid crystal cell>

[0137] Prepare two substrates each formed with a liquid crystal alignment film as described above, and dispose liquid crystal between the two substrates disposed opposite to each other. Specifically, the following two methods can be cited.

[0138] In the first method, first, the two substrates are disposed opposite to each other with a gap (cell gap) therebetween in such a manner that the liquid crystal alignment films face each other. Next, the peripheral portions of the two substrates are bonded using a sealant, and after injecting and filling a liquid crystal composition into the cell gap defined by the substrate surfaces and the sealant and bringing it into contact with the film surface, the injection hole is sealed.

[0139] The above-mentioned liquid crystal composition is not particularly limited, and a composition containing at least one liquid crystal compound (liquid crystal molecule) can be used, and various liquid crystal compositions having a positive or negative dielectric anisotropy. It should be noted that hereinafter, a liquid crystal composition having a positive dielectric anisotropy is also referred to as a positive-type liquid crystal, and a liquid crystal composition having a negative dielectric anisotropy is also referred to as a negative-type liquid crystal.

[0140] The above-mentioned liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxyl group, an amino group, a fluorine atom-containing group (for example, trifluoromethyl), 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) exhibiting liquid crystallinity in the molecule (for example, a bis-mesogenic compound in which two rigid biphenyl structures or terphenyl structures are linked by an alkyl group, etc.). The liquid crystal composition may be a nematic liquid crystal composition, a smectic liquid crystal composition, or a cholesteric liquid crystal composition.

[0141] In addition, from the viewpoint of improving the liquid crystal alignment property, the above-mentioned liquid crystal composition may further contain an additive. Examples of such an additive include a photopolymerizable monomer such as a compound having a polymerizable group (methacryloyl group, etc.); an optically active compound (for example, S-811 manufactured by MERCK Co., Ltd.); an antioxidant; an ultraviolet absorber; a pigment; an antifoaming agent; a polymerization initiator; or a polymerization inhibitor, etc.

[0142] Examples of the positive-type liquid crystal include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, MLC-3019, or MLC-7081 manufactured by MERCK Co., Ltd.

[0143] As negative liquid crystals, for example, MLC-6608, MLC-6609, MLC-6610, MLC-6882, MLC-6886, MLC-7026, MLC-7026-000, MLC-7026-100, or MLC-7029 manufactured by MERCK & Co., Inc. can be cited.

[0144] In addition, in the PSA mode, as the liquid crystal containing a compound having a polymerizable group, MLC-3023 manufactured by MERCK & Co., Inc. can be cited.

[0145] In addition, the second method is a method called the ODF (One Drop Fill) method. A UV curable sealant is applied, for example, at a specified location on one of the two substrates on which a liquid crystal alignment film is formed. Further, a liquid crystal composition is dropped at several specified locations on the surface of the liquid crystal alignment film. Then, the substrates are bonded to each other with the liquid crystal alignment films facing each other, and the liquid crystal composition is pushed to cover the entire surface of the substrate and come into contact with the film surface. Next, UV light is irradiated onto the entire surface of the substrate to cure the sealant. In either case of using either method, it is desirable to further heat to a temperature at which the liquid crystal composition used becomes isotropic, and then slowly cool to room temperature, thereby removing the flow alignment during liquid crystal filling.

[0146] It should be noted that in the case where the coating film is subjected to rubbing alignment treatment, the two substrates are arranged to face each other such that the rubbing directions of the respective coating films form a specified angle, for example, an orthogonal or antiparallel angle.

[0147] As the sealant, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. As the liquid crystal, nematic liquid crystals and smectic liquid crystals can be cited, and nematic liquid crystals are preferred.

[0148] The liquid crystal aligning agent of the present invention is also preferably used for the following liquid crystal display element (PSA mode liquid crystal display element): having a liquid crystal layer between a pair of substrates provided with electrodes, arranging a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates, applying a voltage between the electrodes, and manufacturing through a step of polymerizing the polymerizable compound by irradiating active energy rays and heating at least one of them.

[0149] In addition, the liquid crystal aligning agent of the present invention is also preferably used for the following liquid crystal display element (SC-PVA mode liquid crystal display element): having a liquid crystal layer between a pair of substrates provided with electrodes, arranging a liquid crystal alignment film containing a polymerizable group polymerized by at least one of active energy rays and heat between the pair of substrates, and manufacturing through a step of applying a voltage between the electrodes.

[0150] <Process (4-2): Case of a PSA-mode liquid crystal display element>

[0151] This is carried out in the same manner as in the above (4), except that a liquid crystal composition containing a polymerizable compound is injected or dropped. As the polymerizable compound, for example, a polymerizable compound having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule can be cited.

[0152] <Process (4-3): Case of an SC-PVA-mode liquid crystal display element>

[0153] It is also possible to use a method of manufacturing a liquid crystal display element by performing the same process as in the above (4) and then performing a process of irradiating ultraviolet rays described later. According to this method, similar to the case of manufacturing the above PSA-mode liquid crystal display element, a liquid crystal display element with excellent response speed can be obtained with a small amount of light irradiation. The compound having a polymerizable group can be a compound having one or more of the above polymerizable unsaturated groups in the molecule, and its content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of all polymer components. In addition, the polymer used in the liquid crystal aligning agent can have the above polymerizable group. As such a polymer, for example, a polymer obtained by using a diamine component in the reaction can be cited, and the above diamine component includes a diamine having the above photopolymerizable group at the terminal.

[0154] <Process (4-4): Process of irradiating ultraviolet rays>

[0155] The liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of a pair of substrates obtained in the above (4-2) or (4-3). The voltage applied here can be, for example, a direct current or an alternating current of 5 to 50 V. In addition, as the light for irradiation, for example, ultraviolet rays and visible light containing light with a wavelength of 150 to 800 nm can be used, and ultraviolet rays containing light with a wavelength of 300 to 400 nm are preferred. As the light source for irradiation, 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, an excimer laser, etc. can be used. The light irradiation amount is preferably 1000 to 200000 J / m 2 and more preferably 1000 to 100000 J / m 2 .

[0156] Furthermore, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. As the polarizing plate attached to the outer surface of the liquid crystal cell, a polarizing plate formed by sandwiching a polarizing film called an "H film" with an acetate fiber protective film can be cited; or a polarizing plate composed of the H film itself, and the above H film is formed by stretching and orienting polyvinyl alcohol and absorbing iodine.

[0157] Examples

[0158] Examples are listed below to further illustrate the present invention in detail, but the present invention is not limited to these examples. The abbreviations of the compounds used and the measurement methods of each property are as described below.

[0159] (Solvent)

[0160] NMP: N-methyl-2-pyrrolidone.

[0161] BCS: ethylene glycol monobutyl ether.

[0162] DMF: N,N-dimethylformamide.

[0163] DMAc: N,N-dimethylacetamide.

[0164] THF: tetrahydrofuran.

[0165] IPA: 2-propanol.

[0166] (Tetracarboxylic dianhydride)

[0167] CA-1: The compound represented by the following formula (CA-1).

[0168]

[0169] (Diamine)

[0170] DA-1 to DA-7: Compounds represented by the following formulas (DA-1) to (DA-7), respectively. The diamines contained in the range of the specific diamines of the present invention are the compounds represented by the following formulas (DA-1), (DA-2), and (DA-7).

[0171]

[0172] <Measurement of molecular weight>

[0173] Measurement was carried out using the following normal temperature GPC (gel permeation chromatography) apparatus, and Mn and Mw were calculated in the form of polyethylene glycol and polyethylene oxide conversion values.

[0174] GPC apparatus: GPC-101 (manufactured by Showa Denko K.K.), chromatographic columns: tandem of GPC KD-803 and GPC KD-805 (manufactured by Showa Denko K.K.), column temperature: 50 °C, eluent: N,N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr·H2O) is 30 mmol / L, anhydrous phosphoric acid crystal (orthophosphoric acid) is 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L), flow rate: 1.0 mL / minute.

[0175] Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights; approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by TOSOH Corporation) and polyethylene glycol (molecular weights; approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

[0176] [Synthesis of monomers]

[0177] DA-1 was purchased and used as a commercially available product (manufactured by Chemieliva Pharmaceutical).

[0178] DA-2 was synthesized using the synthesis method described in Journal of Molecular Structure (2018), 1169, 46 - 58.

[0179] DA-6 and DA-7 are novel compounds not disclosed in the literature, etc. The synthesis methods are described in detail below.

[0180] (Synthesis example 1 of monomers; Synthesis of DA-6)

[0181] DA-6 was synthesized according to the route shown below.

[0182]

[0183] To 3-(4-nitrophenoxy)propan-1-ol (manufactured by Chemieliva Pharmaceutical, 16.0 g, 81.1 mmol), dichloromethane (320 g) was added to dissolve it, and then it was cooled under ice-cooling. Triethylamine (12.3 g, 122 mmol), methanesulfonyl chloride (9.76 g, 85.2 mmol), and 4-dimethylaminopyridine (1.0 g, 8.1 mmol) were added thereto, and the mixture was stirred at room temperature for 15 hours to react. Pure water (160 g) was added to the reaction solution, and liquid separation was performed to recover the organic layer, which was washed by liquid separation in the order of 1 equivalent of hydrochloric acid (80 g) and pure water (80 g), and the organic layer was concentrated to obtain DA-6-1 (yield 20.8 g, 75.4 mmol, yield 93%).

[0184]

[0185] To 2,6-dihydroxynaphthalene (5.00 g, 31.2 mmol), NMP (50 g), DA-6-1 (18.9 g, 68.7 mmol), and potassium carbonate (10.8 g, 78 mmol) were added, and the mixture was stirred at 100 °C for 18 hours to allow the reaction to proceed. Pure water (100 g) was added to the reaction solution to precipitate crystals. The obtained crystals were filtered out, washed by repulping with pure water, and then completely dissolved in DMF (500 g) at 100 °C. Crystallization was carried out using methanol / water (1:1, volume ratio) to obtain DA-6-2 (yield: 15.2 g, 29.3 mmol, yield: 94%).

[0186]

[0187] To DA-6-2 (5.00 g, 9.64 mmol), DMF (50 g) and palladium on carbon (5% Pd carbon powder (50% water-containing product), type K, manufactured by N.E. CHEMCAT Corporation, 0.50 g) were added, and the mixture was stirred at 80 °C under a hydrogen atmosphere and under a pressurized condition (0.3 MPa) for 12 hours. Since crystals precipitated, additional DMF (100 g) was added, and the palladium on carbon was removed by filtration. IPA (150 g) was added to the obtained filtrate to effect crystallization, thereby obtaining DA-6 (3.76 g, 8.20 mmol, yield: 85%).

[0188] (Monomer Synthesis Example 2; Synthesis of DA-7)

[0189] DA-7 was synthesized according to the route shown below.

[0190]

[0191] In a 500 mL four-necked flask, p-dichlorobenzyl (7.0 g, 40 mmol) was dissolved in DMAc (140 g), 4-nitro-m-cresol (12.8 g, 84 mmol) and potassium carbonate (16.5 g, 120 mmol) were added, and the mixture was stirred at 90 °C for 3 hours to allow the reaction to proceed. After the reaction solution was cooled to room temperature, pure water (280 g) was added with stirring to precipitate crystals. The obtained crystals were filtered out, and the filter cake was washed in the order of pure water, THF, and acetonitrile (35 g each). Then, it was dried under reduced pressure at 40 °C to obtain DA-7-1 (yield: 15.5 g, 38 mmol, white solid, yield: 95%). Based on the 1 results of 1H-NMR shown below, it was confirmed that this solid was DA-7-1.

[0192] 1H-NMR (500 MHz) in DMSO-d6: δ (ppm) = 8.06 (d, 2H), 7.50 (s, 4H), 7.15 (d, 2H), 7.06 (s, 2H), 5.25 (s, 4H), 2.55 (s, 6H).

[0193]

[0194] Under a nitrogen atmosphere, DA-7-1 (15.5 g, 38 mmol) obtained above, DMF (466 g), and carbon-supported platinum (3% Pt carbon powder (50% water-containing product), manufactured by Evonik Corporation, 1.5 g) were added to a 1 L four-necked flask. After replacing with a hydrogen atmosphere, the mixture was stirred at 50 °C for 18 hours to cause a reaction. After completion of the reaction, the carbon-supported platinum was removed using a membrane filter, and the filtrate was concentrated. IPA (150 g) was added to precipitate crystals, and after stirring at room temperature, the crystals were filtered out. The obtained crystals were washed with IPA (75 g) as a filter cake and dried under reduced pressure at 40 °C, whereby DA-7 (yield: 10.8 g, 31 mmol, gray solid, yield: 81%) was obtained. Based on the 1 results of H-NMR shown below, it was confirmed that this solid was DA-7.

[0195] 1 H-NMR (500 MHz) in DMSO-d6: δ (ppm) = 7.39 (4H, s), 6.66 - 6.51 (6H, m), 4.93 (4H, s), 4.38 (4H, s), 2.02 (6H, s).

[0196] [Synthesis of Polymer]

[0197] <Synthesis Example 1>

[0198] DA-3 (0.541 g, 5.00 mmol), DA-1 (1.60 g, 5.00 mmol), and NMP (15.7 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and the mixture was stirred at room temperature while introducing nitrogen to dissolve it. Then, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added, and the mixture was stirred at 40 °C for 24 hours, whereby a solution of polyamic acid (PAA-1) with a solid component concentration of 12% by mass was obtained. The Mn of this polyamic acid was 13,500 and the Mw was 39,800.

[0199] <Synthesis Example 2>

[0200] To a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, DA-3 (0.541 g, 5.00 mmol), DA-2 (1.98 g, 5.00 mmol), and NMP (18.5 g) were added, and the mixture was stirred at room temperature while nitrogen was being fed to dissolve it. Then, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added, and the mixture was stirred at 40 °C for 24 hours, thereby obtaining a solution of polyamic acid (PAA-2) with a solid component concentration of 12% by mass. The Mn of this polyamic acid was 14,600, and the Mw was 45,600.

[0201] <Synthesis Example 3>

[0202] To a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, DA-3 (0.541 g, 5.00 mmol), DA-4 (1.46 g, 5.00 mmol), and NMP (14.7 g) were added, and the mixture was stirred at room temperature while nitrogen was being fed to dissolve it. Then, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added, and the mixture was stirred at 40 °C for 24 hours, thereby obtaining a solution of polyamic acid (PAA-3) with a solid component concentration of 12% by mass. The Mn of this polyamic acid was 10,900, and the Mw was 29,700.

[0203] <Synthesis Example 4>

[0204] To a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, DA-3 (0.541 g, 5.00 mmol), DA-5 (1.22 g, 5.00 mmol), and NMP (12.9 g) were added, and the mixture was stirred at room temperature while nitrogen was being fed to dissolve it. Then, CA-1 (2.12 g, 9.45 mmol) and NMP (15.5 g) were added, and the mixture was stirred at 40 °C for 24 hours, thereby obtaining a solution of polyamic acid (PAA-4) with a solid component concentration of 12% by mass. The Mn of this polyamic acid was 11,200, and the Mw was 28,500.

[0205] <Synthesis Example 5>

[0206] To a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, DA-3 (0.541 g, 5.00 mmol), DA-6 (2.29 g, 5.00 mmol), and NMP (20.8 g) were added, and the mixture was stirred at room temperature while nitrogen was being fed to dissolve it. Then, CA-1 (2.15 g, 9.60 mmol) and NMP (15.8 g) were added, and the mixture was stirred at 40 °C for 24 hours, thereby obtaining a solution of polyamic acid (PAA-5) with a solid component concentration of 12% by mass. The Mn of this polyamic acid was 18,400, and the Mw was 139,800.

[0207] <Synthesis Example 6>

[0208] DA-3 (0.541 g, 5.00 mmol), DA-7 (1.74 g, 5.00 mmol) and NMP (16.7 g) were added to a 50 mL four-necked flask equipped with a stirring device and a nitrogen inlet tube, and dissolved by stirring at room temperature while nitrogen was being fed. Then, CA-1 (2.13 g, 9.49 mmol) and NMP (15.6 g) were added, and the mixture was stirred at 40 °C for 24 hours to obtain a solution of polyamic acid (PAA-6) with a solid component concentration of 12% by mass. The Mn of this polyamic acid was 11,900 and the Mw was 30,400.

[0209] The specifications of the polyamic acid solution obtained in the above synthesis example are shown in Table 1. In Table 1, the values in parentheses for the tetracarboxylic acid component and the diamine component represent the amounts used (mole parts) of each tetracarboxylic acid component and each diamine component relative to 100 mole parts of the total amount of the diamine components used in each polymerization step.

[0210] [Table 1]

[0211]

[0212] [Preparation of Liquid Crystal Alignment Agent]

[0213] <Example 1>

[0214] NMP (14.0 g) and BCS (6.00 g) were added to the solution (10.0 g) of the polyamic acid (PAA-1) obtained in Synthesis Example 1 above, and the mixture was stirred at room temperature for 30 minutes to obtain a liquid crystal alignment agent (AL-1).

[0215] <Examples 2-3, Comparative Examples 1-3>

[0216] Except that the solution of the polyamic acid used was replaced from (PAA-1) with (PAA-2) to (PAA-6), the same procedure as in Example 1 was carried out to obtain liquid crystal alignment agents (AL-2) to (AL-6).

[0217] The specifications of the liquid crystal alignment agents obtained in the above examples and comparative examples are shown in Table 2.

[0218] [Table 2]

[0219]

[0220] It was confirmed that no abnormalities such as turbidity or precipitation were observed in the liquid crystal alignment agents (AL-1) to (AL-6) obtained as described above, and they were homogeneous solutions. The in-plane uniformity of the contrast and the water contact angle were evaluated using the obtained liquid crystal alignment agents.

[0221] [Fabrication of Liquid Crystal Cell]

[0222] The liquid crystal cell was fabricated in the following order using the liquid crystal aligning agent obtained above. After filtering the liquid crystal aligning agent through a filter with a pore size of 1.0 μm, it was coated on a glass substrate with ITO electrodes (length 40 mm × width 30 mm × thickness 0.7 mm) by spin coating. After drying for 60 seconds on a hot plate at 80 °C, firing was carried out in an infrared heating furnace at 230 °C for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. The coating surface was irradiated with linearly polarized ultraviolet light with a wavelength of 254 nm and an extinction ratio of 26:1 at any one of 400 mJ / cm 2 or 600 mJ / cm 2 or 800 mJ / cm 2 to perform the alignment treatment. Further, firing was carried out in an infrared heating furnace at 230 °C for 30 minutes to obtain a substrate with a liquid crystal alignment film (first glass substrate). The alignment treatment was carried out in such a way that the alignment direction was orthogonal to the first glass substrate. Except for this, a substrate with a liquid crystal alignment film (second glass substrate) was obtained in the same manner as above. Using the above two substrates as a set, bead spacers with a diameter of 4 μm (manufactured by JGC Catalysts & Chemicals Ltd., Silk Ball, SW-D1) were coated on one of the liquid crystal alignment films, and a sealant (manufactured by Mitsui Chemicals, Inc., XN-1500T) was printed around except for the liquid crystal injection port. Another substrate was bonded with the liquid crystal alignment film surface facing each other and the alignment direction being 0°. Then, a heat treatment was carried out at 150 °C for 60 minutes to cure the sealant and fabricate an empty cell. Liquid crystal MLC-3019 (manufactured by MERCK & Co., Inc.) was injected into the empty cell by a reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Then, the obtained liquid crystal cell was heated at 120 °C for 1 hour and used for evaluation.

[0223] [Evaluation of In-Plane Uniformity of Contrast Ratio]

[0224] An AxoStep manufactured by AXOMETRICS, Inc. was used to evaluate the non-uniformity of the twist angle of the liquid crystal cell. The liquid crystal cell fabricated above was set on the measurement stage, and the distribution of Circular Retardance in the pixel plane was measured in a state where no voltage was applied, and 3σ, which is three times the standard deviation σ, was calculated. It can be said that the smaller the value of 3σ, the better the in-plane uniformity. As the evaluation criterion, the case where the above 3σ value is 3.00 or less was set as "○", the case where the above 3σ value is greater than 3.00 and 5.00 or less was set as "△", and the case where the above 3σ value is greater than 5.00 was set as "×". The results are shown in Table 3.

[0225] [Evaluation of Water Contact Angle]

[0226] After filtering the obtained liquid crystal aligning agent with a filter having a pore size of 1.0 μm, it was coated on a glass substrate with an ITO electrode (40 mm in length × 30 mm in width × 1.1 mm in thickness) by spin coating. After drying for 60 seconds on a hot plate at 80 °C, firing was carried out in an infrared heating furnace at 230 °C for 20 minutes to form a liquid crystal alignment film with a film thickness of 100 nm. To this coated film surface, linearly polarized ultraviolet light with a wavelength of 254 nm and an extinction ratio of 26:1 was irradiated through a polarizer, and further firing was carried out in an infrared heating furnace at 230 °C for 30 minutes to obtain a substrate with a liquid crystal alignment film. For this substrate, the contact angle of water was measured using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-701). As an evaluation criterion, when the water contact angle was greater than 50°, it was set as "○", and when the water contact angle was 50° or less, it was set as "×". The results are shown in Table 3. 2 Irradiate linearly polarized ultraviolet light with a wavelength of 254 nm and an extinction ratio of 26:1 through a polarizer, and further fire in an infrared heating furnace at 230 °C for 30 minutes to obtain a substrate with a liquid crystal alignment film. For this substrate, the contact angle of water was measured using a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., DM-701). As an evaluation criterion, when the water contact angle was greater than 50°, it was set as "○", and when the water contact angle was 50° or less, it was set as "×". The results are shown in Table 3.

[0227] [Table 3]

[0228]

[0229] As shown in Table 3, compared with the liquid crystal alignment films obtained using the liquid crystal aligning agents (AL-1), (AL-2), and (AL-6) of Examples 1 to 3, the liquid crystal alignment films obtained using the liquid crystal aligning agents (AL-3) to (AL-5) of Comparative Examples 1 to 3 showed good in-plane uniformity in a wide exposure amount range and had a high water contact angle.

[0230] Industrial Applicability

[0231] The liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is widely used in liquid crystal display elements in various operation modes. For example, it can also be used as a liquid crystal alignment film for a retardation film, a scanning antenna, a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive-scattering type liquid crystal dimming element.

[0232] The liquid crystal display element of the present invention can be effectively applied to devices having various functions. For example, it can be used for liquid crystal TVs, clocks, portable game consoles, word processors, laptop computers, car navigation systems, portable video cameras (camcorders), PDAs (Personal Digital Assistants), digital cameras, mobile phones, smart phones, various monitors, information displays, etc.

[0233] It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-177004 filed on October 28, 2021, and the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2021-189679 filed on November 22, 2021 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A liquid crystal aligning agent, characterized in that Containing at least one polymer (P) selected from the group consisting of a polyimide precursor obtained from a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide which is an imidized product of the polyimide precursor Ar represents any divalent aromatic group among a divalent benzene ring, a biphenyl structure, or a naphthalene ring, and any hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring is optionally substituted by a monovalent group; m and n are each independently an integer from 1 to 3, and any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded is optionally substituted by a monovalent group.

2. The liquid crystal aligning agent according to claim 1, wherein the Ar is selected from 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, biphenyl-4,4'-diyl, 2-methylbiphenyl-4,4'-diyl, 2-ethylbiphenyl-4,4'-diyl, 2-propylbiphenyl-4,4'-diyl, 2-methoxybiphenyl-4,4'-diyl, 2-ethoxybiphenyl-4,4'-diyl, 2-fluorobiphenyl-4,4'-diyl, 3-methylbiphenyl-4,4'-diyl, 3-ethylbiphenyl-4,4'-diyl, 3-propylbiphenyl-4,4'-diyl, 3-methoxybiphenyl-4,4'-diyl, 3-ethoxybiphenyl-4,4'-diyl, 3-fluorobiphenyl-4,4'-diyl, 2,2'-dimethylbiphenyl-4,4'-diyl, 3,3'-dimethylbiphenyl-4,4'-diyl, biphenyl-3,3'-diyl, 5-methylbiphenyl-3,3'-diyl, 5,5'-dimethylbiphenyl-3,3'-diyl, 1,5-naphthylene, 2,6-naphthylene, or 1-methyl-2,6-naphthylene.

3. The liquid crystal aligning agent according to claim 1 or 2, wherein The diamine (0) is any diamine selected from the group consisting of the following formulas (d A -1) to (d A -3), In the formula (d A -1) to (d A -3), any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded, the benzene ring bonded to the alkylene group, the biphenyl structure, or the naphthalene ring is optionally substituted with a monovalent group; m and n each independently have the defined meanings.

4. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein at least one hydrogen atom on the benzene ring to which the amino groups at both ends are bonded is substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, or a fluoroalkoxy group having 1 to 3 carbon atoms.

5. The liquid crystal aligning agent according to any one of claims 1 to 4, wherein the polymer (P) is a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1), In formula (1), X1 represents a tetravalent organic group; Y1 is a divalent organic group obtained by removing two amino groups from the diamine (0) represented by the formula (DA); R and Z each independently represent a hydrogen atom or a monovalent organic group.

6. The liquid crystal aligning agent according to any one of claims 1 to 5, wherein The polymer (P) is obtained by a polycondensation reaction of the diamine component and a tetracarboxylic acid component containing an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof.

7. The liquid crystal aligning agent according to any one of claims 1 to 6, wherein the amount of the diamine (0) used is 5 mol% or more based on the diamine component.

8. The liquid crystal aligning agent according to any one of claims 1 to 7, wherein the liquid crystal aligning agent further contains a polymer (B), and the polymer (B) is at least one selected from the group consisting of a polyimide precursor obtained by using a diamine component not containing the diamine (0) and a polyimide which is an imidized product of the polyimide precursor.

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

10. A liquid crystal display element including the liquid crystal alignment film according to claim 9.

11. A method for manufacturing a liquid crystal display element, including the following steps (1) to (3), Step (1): A step of coating the liquid crystal aligning agent according to any one of claims 1 to 8 on a substrate; Step (2): A step of firing the coated liquid crystal aligning agent to obtain a film; and Step (3): A step of subjecting the film obtained in step (2) to an alignment treatment.

12. The method for manufacturing a liquid crystal display element according to claim 11, wherein the alignment treatment is a photoalignment treatment.

13. A polymer, characterized in that The polymer is at least one polymer (P) selected from the group consisting of a polyimide precursor obtained by using a diamine component containing a diamine (0) represented by the following formula (D A ) and a polyimide which is an imidized product of the polyimide precursor Ar represents any divalent aromatic group among a divalent benzene ring, a biphenyl structure, or a naphthalene ring, and any hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring is optionally substituted with a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluoroalkyl group having 1 to 3 carbon atoms, a fluoroalkenyl group having 2 to 3 carbon atoms, a fluoroalkoxy group having 1 to 3 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 to 3 carbon atoms, a cyano group, and a nitro group; m and n are each independently an integer of 1 to 3, and any hydrogen atom on the benzene ring to which the amino groups at both ends are bonded is optionally substituted with a monovalent group.

14. The polymer according to claim 13, wherein Ar is selected from 1,4-phenylene, 1,3-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, 2-propyl-1,4-phenylene, 2-isopropyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-ethoxy-1,4-phenylene, 2-propoxy-1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-dimethyl-1,4-phenylene, 4-methyl-1,3-phenylene, 5-methyl-1,3-phenylene, 4-fluoro-1,3-phenylene, 2,3,5,6-tetramethyl-1,4-phenylene, biphenyl-4,4'-diyl, 2-methylbiphenyl-4,4'-diyl, 2-ethylbiphenyl-4,4'-diyl, 2-propylbiphenyl-4,4'-diyl, 2-methoxybiphenyl-4,4'-diyl, 2-ethoxybiphenyl-4,4'-diyl, 2-fluorobiphenyl-4,4'-diyl, 3-methylbiphenyl-4,4'-diyl, 3-ethylbiphenyl-4,4'-diyl, 3-propylbiphenyl-4,4'-diyl, 3-methoxybiphenyl-4,4'-diyl, 3-ethoxybiphenyl-4,4'-diyl, 3-fluorobiphenyl-4,4'-diyl, 2,2'-dimethylbiphenyl-4,4'-diyl, 3,3'-dimethylbiphenyl-4,4'-diyl, biphenyl-3,3'-diyl, 5-methylbiphenyl-3,3'-diyl, 5,5'-dimethylbiphenyl-3,3'-diyl, 1,5-naphthylene, 2,6-naphthylene, or 1-methyl-2,6-naphthylene.

15. The polymer according to claim 13 or 14, wherein the polymer (P) is obtained by a polycondensation reaction of the diamine component with a tetracarboxylic acid component containing an acyclic aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or a derivative thereof.

16. The polymer according to claim 13 or 14, wherein the polymer (P) is obtained by a polymerization reaction of the diamine component with a tetracarboxylic acid component containing 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-difluoro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-bis(trifluoromethyl)-1,2,3,4-cyclobutanetetracarboxylic dianhydride, or a derivative thereof.

17. The polymer according to claim 13 or 14, wherein The diamine component further includes a diamine selected from p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 4,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, the diamines represented by the following formula (d AL -1) to (d AL -10), 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, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)diphenyl ether, 1,4-bis[4-(4-aminophenoxy)phenoxy]benzene, 1,2-bis(6-amino-2-naphthyloxy)ethane, 1,2-bis(6-amino-2-naphthyl)ethane, 6-[2-(4-aminophenoxy)ethoxy]-2-naphthylamine, 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, In formula (d AL -6) and (d AL -8), m1 and m2 each independently have the above definitions.

18. The polymer according to claim 13 or 14, wherein the polymer (P) is a polymer having at least one repeating unit selected from the group consisting of a repeating unit (p1) represented by the following formula (1) and an imidized structural unit of the repeating unit (p1). In formula (1), X1 represents a tetravalent organic group; Y1 is a divalent organic group obtained by removing two amino groups from the diamine (0) represented by the formula (DA); R and Z each independently represent a hydrogen atom or a monovalent organic group.

19. A diamine represented by the following formula DA-7,

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