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

Abstract

The present invention provides: a liquid crystal aligning agent which enables the formation of a liquid crystal alignment film that has high refractive index but does not have coloring properties, thereby having high light transmittance; a liquid crystal alignment film which is obtained from this liquid crystal aligning agent; and a liquid crystal display element which comprises this liquid crystal alignment film.　A liquid crystal aligning agent characterized by containing at least one polymer (P) selected from the group consisting of a polyimide precursor obtained using a diamine component including a diamine (0) having the partial structure represented by the formula (DT), and a polyimide which is an imidization product of the polyimide precursor. (R represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, or a C1-4 monovalent organic group. The symbol * represents a bond. Any hydrogen atom of a benzene ring bonded to * may be substituted with a monovalent group. L1 and L2 each independently represent a single bond, -(CH2)n-NR'- (n being an integer of 1-6), -NR'-, -(CH2)n-NR'- (n being an integer of 1-6), -O-, -S-, -O-CO-, or -CO-O-, R' representing a hydrogen atom or a monovalent organic group.)

Description

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

[0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film obtained from the liquid crystal aligning agent, a liquid crystal display device having the liquid crystal alignment film, and a novel diamine and polymer suitable for them.

[0002] Liquid crystal display elements are widely used in a wide range of applications, from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors. Liquid crystal display elements are generally constructed by arranging a pair of electrode substrates facing each other with a predetermined gap (several μm) between them and sealing liquid crystal between the electrode substrates. Images are displayed on the liquid crystal display element by applying a voltage between the transparent conductive films constituting the electrodes of the electrode substrates. These liquid crystal display elements have a liquid crystal alignment film, which is essential for controlling the alignment state of liquid crystal molecules. Patent Document 1 discloses a polyimide alignment film obtained using a diamine compound with a specific structure containing a triazine ring, as a liquid crystal alignment film that can easily adjust the pretilt angle of liquid crystal molecules.

[0003] Meanwhile, various driving methods have been developed for liquid crystal display elements, which differ in electrode structure, physical properties of the liquid crystal molecules used, etc. For example, various modes are known, such as the twisted nematic (TN) method, the super twisted nematic (STN) method, the vertical alignment (VA) method, the in-plane switching (IPS) method, and the fringe field switching (FFS) method. VA (vertical alignment) liquid crystal display elements have a wide viewing angle, a fast response speed, and high contrast, and do not require a rubbing treatment in the production process, so they are widely used, especially for televisions and monitors, for which there is a high demand for larger displays (Patent Documents 2 and 3).

[0004] Japanese Patent Publication No. 2006-511696 Japanese Patent Publication No. 2008-76950 International Publication No. 2008 / 117615

[0005] The transparent conductive film in a liquid crystal display element is typically formed from a composition (ITO) primarily composed of indium oxide doped with a few percent tin oxide. Its refractive index, however, is higher than that of the liquid crystal alignment film. Therefore, when light from a display light source is transmitted through the electrode substrate, the light is reflected at the interface between the transparent conductive film and the liquid crystal alignment film on each electrode substrate. As a result, the light transmittance of the electrode substrate is insufficient, resulting in reduced display brightness. In particular, ultra-high-definition panels, such as 4K and 8K, have been developed in recent years. However, these panels require a large occupancy rate for black matrices (BMs) and thin film transistors (TFTs), reducing the aperture ratio of the panel. Therefore, improving the transmittance of the display area is becoming increasingly important.

[0006] Therefore, the present inventors have investigated various materials for forming a liquid crystal alignment film, with the view that the above-mentioned problems can be resolved by reducing the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film. Polyamic acid or its derivative, polyimide, is widely known as a material for forming a liquid crystal alignment film. The use of a diamine having a triazine skeleton as a diamine component in the raw material for a polyimide liquid crystal alignment film has been proposed, for example, in Patent Document 1. However, the present inventors have found that the method specifically disclosed in Patent Document 1, which uses a diamine having a polycyclic structure, such as a long-chain alkyl group or cholesterol, and a triazine skeleton, leaves room for improvement in terms of increasing the refractive index. Specifically, in order to increase the refractive index of the liquid crystal alignment film, various types of polymers to be contained in the liquid crystal aligning agent forming the liquid crystal alignment film have been explored.

[0007] As a result, by selecting a specific polymer, it was possible to obtain a liquid crystal alignment film having a refractive index close to that of the transparent conductive film, but on the other hand, it was revealed that polymers forming a liquid crystal alignment film with a high refractive index often have coloring properties. A liquid crystal alignment film formed from a liquid crystal alignment agent containing a coloring polymer has low light transmittance, which leads to a decrease in display brightness, and as a result, the above-mentioned object cannot be achieved.

[0008] In view of the above circumstances, an object of the present invention is to provide a liquid crystal alignment agent that forms a liquid crystal alignment film having a high refractive index but no coloring property and therefore high light transmittance, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film.

[0009] The present inventors have conducted extensive research to achieve the above object, and have found that a liquid crystal aligning agent containing a novel polymer having a specific structure is effective for achieving the above object, thereby completing the present invention. Ｔ and a polyimide obtained by imidizing the polyimide precursor; a liquid crystal alignment film obtained from the liquid crystal alignment agent; and a liquid crystal display element having the liquid crystal alignment film. (wherein R represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms; * represents a bond, and any hydrogen atom of the benzene ring bonded to * may be replaced with a monovalent group; L １ and L ２ are each independently a single bond, -(CH ２ ) ｎ -(n is an integer of 1 to 6), -NR'-, -(CH ２ ) ｎ represents —NR′— (n is an integer of 1 to 6), —O—, —S—, —O—CO—, or —CO—O—, and R′ represents a hydrogen atom or a monovalent organic group.) Throughout this specification, examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and * represents a bond.

[0010] According to the present invention, a liquid crystal aligning agent is obtained that has a high refractive index but is not colorable, and therefore forms a liquid crystal alignment film with high light transmittance. Because the liquid crystal alignment film formed with such a liquid crystal aligning agent has a high refractive index, the difference between the refractive index of the transparent conductive film in a liquid crystal display element and the refractive index of the liquid crystal alignment film can be reduced. Furthermore, because it is not colorable, a liquid crystal display element with high light transmittance and high display brightness can be obtained.

[0011] As described above, the liquid crystal aligning agent of the present invention is a compound represented by the following formula (D Ｔ The composition is characterized in that it contains at least one polymer (P) selected from the group consisting of polyimide precursors obtained using a diamine component containing diamine (0) (hereinafter also referred to as specific diamine) having a partial structure represented by the formula: The above formula (D Ｔ ) in which R, L １ , and L ２ are as defined above.

[0012] The above formula (D Ｔ Examples of the monovalent organic group having 1 to 4 carbon atoms for R in (a) include a hydrocarbon group having 1 to 4 carbon atoms and a monovalent organic group (E) containing a heteroatom-containing group (such as —O—, —S—, —C(═O)—, —C(═O)—O—, —O—C(═O)—, —NR″—, —NR″-C(═O)—, etc.) between carbon-carbon bonds or at least at one end of the hydrocarbon group, and the monovalent organic group (E) is bonded to the triazine ring via a carbon atom of the heteroatom-containing group or hydrocarbon group. Here, R" represents a hydrogen atom or a monovalent organic group such as a methyl group. Specific examples of the hydrocarbon group having 1 to 4 carbon atoms include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group; alkenyl groups having 2 to 4 carbon atoms such as a vinyl group and a propenyl group; and alkynyl groups having 2 to 4 carbon atoms such as an ethynyl group. Some of the hydrogen atoms in the hydrocarbon group having 1 to 4 carbon atoms or the monovalent organic group (E) may be substituted with a substituent, and examples of such substituents include a halogen atom, a hydroxy group, and a cyano group. The halogen atom in R may have the same structure as described above.Ｔ ) represents a bond, and any hydrogen atom of the benzene ring bonded to the * may be replaced with a monovalent group, and specific examples of the monovalent group include a methyl group, an ethyl group, and a methoxy group.

[0013] The above formula (D Ｔ In order to increase the refractive index, the monovalent organic group having 1 to 4 carbon atoms represented by R in the above formula (D) preferably has at least one atom selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Ｔ Specific more preferred examples of R in the above formula (1) include a fluorine atom, a chlorine atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a trifluoromethylthio group, a dimethylamino group, a methyl group, an ethyl group, a vinyl group, an allyl group, a methoxymethyl group, a 2-methoxyethoxymethyl group, an acetyl group, and a hydroxy group.

[0014] The above formula (D Ｔ ) in L １ and L ２ From the viewpoint of suitably obtaining the effects of the present invention, each of the groups independently represents a single bond, —(CH ２ ) ｎ -(n is an integer of 1 to 6), -NR'-, -(CH ２ ) ｎ -NR'- (n is an integer of 1 to 6), -S-, or -O- is preferred, -S-, -NH-, or -O- is more preferred, and -S- is particularly preferred. R' represents a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include a methyl group, a tert-butoxycarbonyl group, an ethyl group, and a propyl group. R' is preferably a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group.

[0015] From the viewpoint of suitably obtaining the effects of the present invention, Ｔ ) in L １ a carbon atom adjacent to the carbon atom constituting the benzene ring bonded to L ２Preferably, at least one carbon atom selected from the group consisting of carbon atoms adjacent to the carbon atom constituting the benzene ring bonded to the nitrogen atom of the triazine ring is bonded to a group capable of forming a hydrogen bond with the nitrogen atom of the triazine ring. The group capable of forming a hydrogen bond is preferably a hydrogen atom. For example, when the group capable of forming a hydrogen bond is a hydrogen atom, a bond as shown in the following formula (M) can be formed, resulting in a stacking effect, which is more effective in increasing the refractive index.

[0016] The above formula (D Ｔ Preferred examples of the partial structure represented by the following formula (d Ｔ -1) to (d Ｔ -3) can be mentioned. (The above formula (d Ｔ -1) to (d Ｔ -3), R and * are each represented by the formula (D Ｔ ) has the same meaning as R and * in

[0017] A preferred specific example of the diamine (0) is a compound represented by the following formula (d ０ ) structure.

[0018]

[0019] The above formula (d ０ In the diamine having the structure of the formula (D Ｔ ) and Ar and Ar' each independently represent a divalent aromatic ring group. Specific examples of the aromatic ring in the divalent aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridine ring. A hydrogen atom in the aromatic ring may be substituted with a monovalent group. Specific examples of the monovalent group include the rings represented by the above formula (D Ｔ ) and the like. ０ ) Medium, L ｄ and L ｄ ' are each independently a single bond, -(CH ２ )ｎ -(n is an integer of 1 to 6), -NR'-, -(CH ２ ) ｎ -NR'- (n is an integer of 1 to 6), -O-, -S-, -O-CO-, or -CO-O-, and R' represents a hydrogen atom or a monovalent organic group. From the viewpoint of suitably obtaining the effects of the present invention, Ar and Ar' are each independently preferably a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, a pyridazine ring, a triazine ring, or a carbazole ring, and more preferably a benzene ring, a naphthalene ring, an anthracene ring, or a triazine ring. Ld and Ld' are each independently preferably -NR'-, -O-, -S-, -O-CO-, or -CO-O-, and more preferably -NR'-, -O-, or -S-. R' is preferably a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group. Furthermore, m and m' are each independently an integer of 0 to 2, preferably 0 or 1. Ar, Ar', L ｄ and L ｄ When there are a plurality of Ar, Ar', L ｄ and L ｄ ' may be the same or different.

[0020] The above formula (d ０ As the diamine having the structure of the following formula (D), for example, ＴＳ ) is an example of a diamine having a structure represented by the formula: (Formula (D ＴＳ In the formula, R represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms. Any hydrogen atom in the benzene ring bonded to the amino group may be replaced with a monovalent group.

[0021] The above formula (d ０ ) is preferably a compound represented by the following formula (d ０ -1) to (d ０ Among them, from the viewpoint of suitably obtaining the effects of the present invention, diamines represented by the formula (d ０ -3), (d ０ -6) and (d ０ Diamines represented by formula (I)-9) are more preferred. (In the above formula, R is the above formula (D Ｔ ) has the same meaning as R in

[0022] (Production of Polymer (P)) The polymer (P) contained in the liquid crystal aligning agent of the present invention is at least one polymer selected from the group consisting of polyimide precursors obtained using a diamine component containing the diamine (0) and polyimides that are imidized products of the polyimide precursors. Here, the polyimide precursor is a polymer that can be obtained by imidizing polyamic acid, polyamic acid ester, or the like. The polyamic acid (P'), which is the polyimide precursor of the polymer (P), can be obtained by polymerization of a diamine component containing the diamine (0) with a tetracarboxylic acid component. The diamine (0) may be used alone or in combination of two or more. In this case, the amount of diamine (0) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, based on the total diamine components.

[0023] The diamine component used in producing the polyamic acid (P') may contain a diamine other than diamine (0) (hereinafter also referred to as "other diamine"). When other diamines are used in addition to the diamine (0), the amount of diamine (0) used relative to the diamine component is preferably 90 mol % or less, more preferably 80 mol % or less. Examples of other diamines are listed below, but the present invention is not limited to these. The other diamines may be used alone or in combination of two or more.

[0024] Diamines represented by the following formula (d1) or formula (d2), p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamines having a carboxy group such as diamine compounds represented by the following formulas (3b-1) to (3b-4), diamines having a photoalignment group such as diamines represented by the following formulas (g-1) to (g-6), 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)benzene ethane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, bis(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)propane, diamines represented by the following formulas (nh-1) to (nh-8), dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoic-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indan-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-6-amine, 1,3-bis(4-aminophenethyl)urea, and compounds having a photopolymerizable group at their terminals, such as those represented by the following formulae (4b-1) to (4b-7). Diamines, diamines having a radical initiating function such as those represented by the following formulae (R1) to (R5), diamines having a photosensitizing function that exhibits a sensitizing effect upon irradiation with light such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 9,9-bis(4-aminophenyl)fluorene, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, and 9-phenyl-3,6-diaminocarbazole. diamines having a heterocycle such as those of the following formulae (z-1) to (z-13); diamines having a diphenylamine skeleton such as those of the following formulae (Dp-1) to (Dp-9); a group "-N(D)-" (D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom. D is preferably a tert-butoxycarbonyl group) or a group "*-L-O-D" (* represents a bond to the nitrogen atom. L represents an alkylene group having 1 to 5 carbon atoms. D represents a protecting group which is eliminated by heating and replaced with a hydrogen atom. D is preferably a tert-butoxycarbonyl group) such as those of the following formulae (5-1) to (5-13). diamines having a siloxane bond such as 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, diamines represented by the following formula (Ds-1), diamines having an oxazoline structure such as those represented by the following formulas (Ox-1) to (Ox-2), aliphatic diamines such as 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,Diamines such as alicyclic diamines such as 3-bis(aminomethyl)cyclohexane.

[0025] (In the above formula (d2), X is a single bond, —O—, —C(CH ３ ) ２ -, -NH-, -CO-, -(CH ２ ) ｍ -, -SO ２ -, -O-(CH ２ ) ｍ -O-, -OC(CH ３ ) ２ -, -CO-(CH ２ ) ｍ -, -NH-(CH ２ ) ｍ -, -SO ２ - (CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -NHCO- or -COO-(CH ２ ) ｍ represents —OCO—, and m is an integer of 1 to 8. In the above formula (d1) or formula (d2), Y represents a structure represented by any one of the following formulas (S1) to (S2). In the above formula (d2), the two Ys may be the same or different.

[0026] (In the above formula (S1), X １ is a single bond, -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ３ )-, -NH-, -O-, -COO-, -OCO- or -((CH ２ ) ａ１ -A １ ) ｍ１ - (a1 is an integer from 1 to 15, A １ represents an oxygen atom or —COO—, m １ is an integer of 1 to 2. １ When is 2, multiple a1 and A １ Each of the groups independently has the same definition as above. １represents a divalent cyclic group selected from divalent aromatic hydrocarbon groups having 6 to 12 carbon atoms and divalent alicyclic hydrocarbon groups having 4 to 8 carbon atoms. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. m is an integer of 1 to 4. When m is 2 or more, multiple X １ , G １ Each independently has the definition above. １ represents a fluorine atom, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms.

[0027] (In the above formula (S2), X ２ is -CONH-, -NHCO-, -O-, -CH ２ O-, -OCH ２ represents -, -COO- or -OCO-. ２ represents a structure having a steroid skeleton. At least one of the hydrogen atoms in the structure having a steroid skeleton may be substituted with a substituent selected from the group consisting of a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group in which any carbon-carbon bond in the halogen-containing alkyl group, halogen-containing alkoxy group, alkyl group having 3 to 10 carbon atoms, alkoxy group having 3 to 10 carbon atoms, and alkenyl group having 3 to 10 carbon atoms is interrupted by an oxygen atom.

[0028] (In (3b-1) above, A １ is a single bond, -CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３)-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CO-N(CH ３ ) - or -N(CH ３ )-CO-, m1 and m2 each independently represent an integer of 0 to 4, and m1+m2 represents an integer of 1 to 4. In formula (3b-2), m3 and m4 each independently represent an integer of 1 to 5. In formula (3b-3), A ２ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 represents an integer of 1 to 5. ３ and A ４ are each independently a single bond, —CH ２ -, -C ２ H ４ -, -C(CH ３ ) ２ -, -CF ２ -, -C(CF ３ ) ２ -, -O-, -CO-, -NH-, -N(CH ３ )-, -CONH-, -NHCO-, -CH ２ O-, -OCH ２ -, -COO-, -OCO-, -CO-N(CH ３ ) - or -N(CH ３ )-CO-, and m6 represents an integer of 1 to 4.

[0029] (In the above formula (g-6), L represents a single bond, an alkylene group having 1 to 15 carbon atoms, or -O-, -COO-, -NH-, -NHCO-, or -CON(CH ３ )-- is inserted (provided that the divalent organic group is bonded to the oxygen atom of the ester bond adjacent to L via a carbon atom), X １ , G １ , and R １ has the same meaning as in formula (S1). m is an integer of 0 to 4. When m is 2 or more, a plurality of X １ and G １are each independently defined as above. In addition, a hydrogen atom on the benzene ring may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom.

[0030]

[0031] (In the above formulas (4b-1) to (4b-6), n1 is an integer of 2 to 12.)

[0032] (In the above formulas (R3) to (R5), n is an integer of 1 to 6.)

[0033]

[0034]

[0035] (In the above formulas (5-1) to (5-13), Boc represents a tert-butoxycarbonyl group.)

[0036]

[0037] In the above formula (S1), G １ Examples of the divalent cyclic group in formula (S2) include a cyclopropylene group, a cyclohexylene group, and a phenylene group. Any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. In formula (S2) above, G ２ The structure having a steroid skeleton in the formula (I) is preferably a structure containing a cholestanyl group, a cholesteryl group or a lanostaniyl group.

[0038] Preferred examples of the diamine represented by the formula (d1) include the following formulas (d1-1) to (d1-6): Preferred examples of the diamine represented by the formula (d2) include the following formulas (d2-1) to (d2-6):

[0039] (In the above formula, X ｖ１ ~X ｖ４ , X ｐ１ ~X ｐ８ are each independently -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH ３ )-, -NH-, -O-, -CH ２ O-, -CH ２ represents —OCO—, —COO—, or —OCO—; X Ｖ５ ~X Ｖ６ , X ｓ１ ~X ｓ４ are each independently —O—, —CH ２ represents —O—, —COO—, or —OCO—. ａ ~X ｆ represents a single bond, —O—, —NH—, or —O—(CH ２ ) ｍ -O- (where m represents an integer of 1 to 8), and R ｖ１ ~R ｖ４ , R １ａ ~R １ｈ are each independently -C ｎ H ２ｎ＋１ (n represents an integer of 3 to 10), or —O—C ｎ H ２ｎ＋１ (n represents an integer of 3 to 10.)

[0040] As the other diamines, from the viewpoint of suitably obtaining the effects of the present invention, diamines represented by formula (d1) or formula (d2), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, diamines having the above-mentioned photoalignment groups, diamines having radical initiation function, diamines having a photopolymerizable group at the terminal, diamines represented by the above-mentioned formulas (z-1) to (z-13), diamines represented by the above-mentioned formulas (5-1) to (5-13), and diamines represented by the above-mentioned formulas (Ox-1) to (Ox-2) are preferred.

[0041] When other diamines are used in addition to the diamine (0), the amount of the other diamines used is preferably 10 to 90 mol %, more preferably 20 to 80 mol %, based on the total diamine components used in the production of the polymer (P).

[0042] (Tetracarboxylic Acid Component) When producing the polyamic acid (P′), the tetracarboxylic acid component to be reacted with the diamine component may be not only a tetracarboxylic acid dianhydride, but also a derivative of a tetracarboxylic acid dianhydride such as a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic acid dialkyl ester, or a tetracarboxylic acid dialkyl ester dihalide.

[0043] The tetracarboxylic dianhydride or derivative thereof may be an acyclic aliphatic tetracarboxylic dianhydride or derivative thereof, an alicyclic tetracarboxylic dianhydride or derivative thereof, or an aromatic tetracarboxylic dianhydride or derivative thereof. Among these, a tetracarboxylic dianhydride having at least one partial structure selected from the group consisting of a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure, and a cyclohexane ring structure, or a derivative thereof, is more preferred. The tetracarboxylic acid component that can be used in the synthesis of the polyimide precursor is preferably a tetracarboxylic dianhydride or derivative thereof represented by the following formula (T). Examples of the derivatives of the tetracarboxylic dianhydride include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides. The tetracarboxylic acid dianhydrides or derivatives thereof may be used alone or in combination of two or more. (In the above formula (T), X represents a structure selected from any of the following formulae (x-1) to (x-13).)

[0044] (In the above formula (x-1), R １ ~R ４each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. ５ and R ６ In the formulae (x-12) and (x-13), j and k each independently represent a hydrogen atom or a methyl group. １ and A ２ each independently represents a single bond, -O-, -CO-, -COO-, a phenylene group, a sulfonyl group, or an amide group. In the above formulae (x-1) to (x-13), *1 is a bond bonded to one acid anhydride group, and *2 is a bond bonded to the other acid anhydride group. In the above formula (x-13), ２ may be the same or different.)

[0045] Preferred specific examples of the above formula (x-1) include the following formulae (X1-1) to (X1-6).

[0046]

[0047] Preferred specific examples of the above formulas (x-12) and (x-13) include the following formulas (x-14) to (x-29).

[0048] Preferred examples of the tetracarboxylic dianhydride represented by the formula (T) or a derivative thereof include tetracarboxylic dianhydrides represented by the formula (T) in which X is any of the formulae (x-1) to (x-7), (x-11) to (x-13), or a derivative thereof, more preferably tetracarboxylic dianhydrides represented by the formula (T) in which X is any of the formulae (x-1) to (x-6), or a derivative thereof.

[0049] The proportion of the tetracarboxylic dianhydride represented by the above formula (T) or its derivative to be used is preferably 10 mol % or more, more preferably 20 mol % or more, and even more preferably 50 mol % or more, based on 1 mol of the total tetracarboxylic acid components used. The tetracarboxylic dianhydride and its derivative to be used in the production of the polyamic acid (P') may contain a tetracarboxylic dianhydride or its derivative other than the above formula (T).

[0050] (Synthesis of Polyamic Acid) Polyamic acid is synthesized by reacting a diamine component containing the diamine described above with a tetracarboxylic acid component containing the tetracarboxylic acid dianhydride or its derivative in an organic solvent. The ratio of the tetracarboxylic acid dianhydride and diamine used in the polyamic acid synthesis reaction is preferably such that 0.5 to 2 equivalents of the acid anhydride groups of the tetracarboxylic acid dianhydride are present per equivalent of the amino groups of the diamine, more preferably 0.8 to 1.2 equivalents. As with typical polycondensation reactions, the closer the equivalent of the acid anhydride groups of the tetracarboxylic acid dianhydride is to 1 equivalent, the higher the molecular weight of the resulting polyamic acid. The reaction temperature in the polyamic acid synthesis reaction is preferably −20 to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours. The polyamic acid synthesis reaction can be carried out at any concentration, but the concentration of polyamic acid in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration in the early stages, and then a solvent can be added.

[0051] Specific examples of the organic solvent include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone. When the polymer has high solubility in the solvent, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by the following formulas [D-1] to [D-3] can be used. (In formula [D-1], D１ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-2], D ２ represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D ３ represents an alkyl group having 1 to 4 carbon atoms.

[0052] Specific examples of the solvents represented by the above formulas [D-1] to [D-3] include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

[0053] (Synthesis of Polyamic Acid Ester) The polyamic acid ester can be obtained by known methods such as, for example, [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, or [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine.

[0054] (Synthesis of Polyimide) Polyimide can be obtained by ring-closing (imidizing) a polyimide precursor such as the polyamic acid or polyamic acid ester. The imidization ratio in this specification refers to the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or its derivatives and carboxyl groups (or their derivatives). The imidization ratio does not necessarily have to be 100% and can be adjusted as desired depending on the application and purpose.

[0055] Methods for imidizing the polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, and catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor.

[0056] When the polyimide precursor is thermally imidized in a solution, the temperature is preferably 100 to 400°C, more preferably 120 to 250°C, and it is preferable to carry out the imidization while removing water produced by the imidization reaction from the system.

[0057] Catalytic imidization of polyimide precursors can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor and stirring at -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is 0.5 to 30 times, preferably 2 to 20 times, the molar ratio of the amic acid groups, and the amount of the acid anhydride is 1 to 50 times, preferably 3 to 30 times, the molar ratio of the amic acid groups. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Of these, pyridine is preferred because it has adequate basicity for promoting the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.

[0058] When recovering the produced polyimide precursor or polyimide from a reaction solution of a polyimide precursor or polyimide, the reaction solution may be precipitated by pouring the reaction solution into a solvent. Examples of solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated by pouring into the solvent can be recovered by filtration and then dried at room temperature or by heating under atmospheric or reduced pressure. Furthermore, the precipitated polymer can be redissolved in an organic solvent and reprecipitated and recovered 2 to 10 times, thereby reducing the amount of impurities in the polymer. Examples of solvents used in this process include alcohols, ketones, and hydrocarbons. Using three or more solvents selected from these solvents is preferred because it further increases the efficiency of purification.

[0059] <End-capping Agent> When synthesizing the polyimide precursor or polyimide of the present invention, an end-capping polymer may be synthesized using a tetracarboxylic acid component containing a tetracarboxylic dianhydride or its derivative, and a diamine component containing the above-mentioned diamine, along with an appropriate end-capping agent. The end-capping polymer has the effect of improving the film hardness of the alignment film obtained by coating and improving the adhesion properties between the sealing agent and the alignment film. Examples of the terminals of the polyimide precursor or polyimide of the present invention include amino groups, carboxy groups, acid anhydride groups, and groups derived from the end-capping agents described below. The amino groups, carboxy groups, and acid anhydride groups can be obtained by a conventional condensation reaction or by blocking the terminals with the following end-capping agents.

[0060] Examples of the end-capping agent include acid anhydrides such as acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-(3-trimethoxysilyl)propyl-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, and 4-ethynylphthalic anhydride; dicarbonate diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; chlorocarbonyl compounds such as acryloyl chloride, methacryloyl chloride, and nicotinic acid chloride; and aniline. Examples of the amino acid ester include monoamine compounds such as 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, and n-octylamine; and isocyanates having an unsaturated bond such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, or 2-acryloyloxyethyl isocyanate and 2-methacryloyloxyethyl isocyanate.

[0061] The proportion of the end-capping agent used is preferably 0.01 to 20 parts by mole, and more preferably 0.01 to 10 parts by mole, per 100 parts by mole of the total of the diamine components used.

[0062] <Molecular Weight and Molecular Weight Distribution of Polyimide Precursor and Polyimide> The polystyrene-equivalent weight average molecular weight (Mw) of the polyimide precursor and polyimide measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. The molecular weight distribution (Mw / Mn), expressed as the ratio of the Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC, is preferably 15 or less, and more preferably 10 or less. Having the molecular weight within this range ensures good alignment in liquid crystal display elements.

[0063] (Liquid Crystal Aligning Agent) The liquid crystal aligning agent of the present invention is a liquid composition obtained by dispersing or dissolving the polymer (P) and other components used as needed, preferably in a suitable solvent.

[0064] The liquid crystal aligning agent of the present invention may contain a polymer other than the polymer (P). Specific examples of the other polymer include at least one polymer selected from the group consisting of polyimide precursors other than the polymer (P) and polyimides which are imidized products of the polyimide precursors, polysiloxane, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-maleic anhydride) copolymer, poly(isobutylene-maleic anhydride) copolymer, poly(vinyl ether-maleic anhydride) copolymer, poly(styrene-phenylmaleimide) derivative, and a polymer selected from the group consisting of poly(meth)acrylate. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, and SMA3000 (manufactured by Cray Valley Corporation), and GSM301 (manufactured by Gifu Ceramics Manufacturing Co., Ltd.). A specific example of a poly(isobutylene-maleic anhydride) copolymer is ISOBAN-600 (manufactured by Kuraray Co., Ltd.). A specific example of a poly(vinyl ether-maleic anhydride) copolymer is Gantrez AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by Ashland Corporation). As the other polymer, from the viewpoint of improving vertical alignment, at least one polymer selected from the group consisting of polyimide precursors obtained using a diamine component containing a diamine represented by formula (d1) or (d2) above and polyimides which are imidized products of the polyimide precursors is preferred. One type of other polymer may be used alone, or two or more types may be used in combination. The content of the other polymers is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and even more preferably 20 to 80 parts by mass, relative to 100 parts by mass of the total of the polymers contained in the liquid crystal aligning agent.

[0065] The liquid crystal aligning agent of the present invention may contain other components in addition to those described above, as necessary. Examples of such components include at least one compound selected from the group consisting of crosslinkable compounds having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group, and an alkoxy group, and crosslinkable compounds having a polymerizable unsaturated group, functional silane compounds, metal chelate compounds, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, and compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film. Preferred specific examples of the crosslinkable compound include compounds represented by the following formulas (CL-1) to (CL-11). The compounds represented by the following formulas (CL-1) to (CL-11) are examples of crosslinkable compounds, and the present invention is not limited to these. The crosslinkable compounds used in the liquid crystal aligning agent of the present invention may be one type, or two or more types may be combined. The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 50 parts by mass, more preferably 1 to 50 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of all polymer components. Examples of compounds for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film include monoamines having a nitrogen-containing aromatic heterocycle such as 3-picolylamine.

[0066] Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N-(n-propyl)-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-(n-butyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone. , 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ethylene glycol monomethyl ether Examples of the olefin copolymer include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, and propylene carbonate. These may be used in combination of two or more.

[0067] The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferably in the range of 1 to 10 mass%. From the viewpoint of forming a uniform and defect-free coating film, 1 mass% or more is preferred, and from the viewpoint of storage stability of the solution, 10 mass% or less is preferred. A particularly preferred polymer concentration is 2 to 8 mass%.

[0068] The liquid crystal alignment film of the present invention is obtained from the liquid crystal aligning agent. The liquid crystal alignment film of the present invention can be used as a horizontal alignment type or vertical alignment type liquid crystal alignment film, and is particularly suitable for a vertical alignment type liquid crystal display element such as a VA mode or PSA (Polymer Sustained Alignment) mode.

[0069] The liquid crystal display element of the present invention is provided with the above-described liquid crystal alignment film. The liquid crystal aligning agent of the present invention is also preferably used for a liquid crystal display element which has a liquid crystal layer between a pair of substrates each having an electrode, and is manufactured by a process of disposing a liquid crystal composition containing a polymerizable compound which is polymerized by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between the electrodes.

[0070] The liquid crystal display element of the present invention can be manufactured, for example, by a method that performs the following steps (1) to (3) or steps (1) to (4) in this order. (1) A step of applying a liquid crystal aligning agent to at least one of a pair of substrates having a conductive film to form a coating film. The liquid crystal aligning agent of the present invention is applied to one surface of at least one of a pair of substrates having a patterned transparent conductive film by an appropriate coating method, such as a roll coater method, a spin coating method, a printing method, or an inkjet method, to form a coating film. The substrate is not particularly limited as long as it is highly transparent. In addition to glass substrates and silicon nitride substrates, plastic substrates such as acrylic substrates and polycarbonate substrates can also be used. Furthermore, in reflective liquid crystal display elements, an opaque material such as a silicon wafer can be used for only one of the substrates. In this case, a light-reflective material such as aluminum can also be used for the electrode.

[0071] (2) Step of Baking the Coating Film After applying the liquid crystal alignment agent, the coating film is baked to prevent dripping of the applied alignment agent. Preferably, preheating (prebaking) is first performed. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Then, a heating (postbaking) step is preferably performed. The postbaking temperature is preferably 80 to 300°C, more preferably 120 to 250°C. The postbaking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.

[0072] The coating film formed in the above steps (1) and (2) can be used as a liquid crystal alignment film as it is, but the coating film may be subjected to an alignment ability imparting treatment, such as a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, or cotton, or a photoalignment treatment in which the coating film is irradiated with polarized or unpolarized radiation.

[0073] In the photo-alignment treatment, the radiation irradiated onto the coating film can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm. When the radiation is polarized, it may be linearly polarized or partially polarized. Furthermore, when the radiation used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When irradiating with unpolarized radiation, the irradiation direction is an oblique direction. (3) Step of forming a liquid crystal layer between the pair of substrates to prepare a liquid crystal cell. (3-1) When manufacturing a VA-mode liquid crystal display element. As described above, two substrates are prepared, at least one of which has the liquid crystal alignment film of the present invention formed thereon, and liquid crystal is disposed between the two substrates arranged opposite each other. Specifically, the following two methods can be used. The first method is a conventionally known method. First, two substrates are arranged opposite each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other. Next, a sealant is applied to the peripheries of the two substrates and they are bonded together, and a liquid crystal composition is injected into the cell gap defined by the substrate surfaces and the sealant to contact the film surface, and then the injection hole is sealed.

[0074] The second method is called the ODF (One Drop Fill) method. A UV-curable sealant, for example, is applied to a predetermined location on one of two substrates on which a liquid crystal alignment film has been formed. A liquid crystal composition is then dropped onto several predetermined locations on the liquid crystal alignment film. The other substrate is then attached so that the liquid crystal alignment film faces the other substrate, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. The entire surface of the substrate is then irradiated with UV light to cure the sealant. In either method, it is desirable to further heat the liquid crystal composition to a temperature at which it assumes an isotropic phase and then slowly cool it to room temperature to remove flow alignment that occurs during liquid crystal filling. The liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used. Hereinafter, liquid crystal compositions with positive dielectric anisotropy are also referred to as positive liquid crystals, and liquid crystal compositions with negative dielectric anisotropy are also referred to as negative liquid crystals. The liquid crystal composition may contain a liquid crystal compound having a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., a trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocycle, a cycloalkane, a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring. It may also contain a compound having two or more rigid moieties (mesogenic skeletons) exhibiting liquid crystallinity within the molecule (e.g., a bimesogenic compound in which two rigid biphenyl structures or terphenyl structures are connected by an alkyl group). The liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a smectic phase, or a cholesteric phase. Furthermore, additives may be further added to the liquid crystal composition to improve the liquid crystal alignment properties. Examples of such additives include photopolymerizable monomers such as compounds having a polymerizable group described below; optically active compounds (e.g., S-811 manufactured by Merck Ltd.); antioxidants; ultraviolet absorbers; dyes; antifoaming agents; polymerization initiators; and polymerization inhibitors. Examples of the positive liquid crystal include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck.Examples of negative liquid crystals include MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck & Co., Inc. In addition, in the PSA mode, an example of a liquid crystal containing a compound having a polymerizable group is MLC-3023 manufactured by Merck & Co., Inc.

[0075] (3-2) In the case of producing a PSA-mode liquid crystal display element, the procedure is the same as in (3-1) above, except that a liquid crystal composition containing a compound having a polymerizable group is injected or dropped. Examples of the compound having a polymerizable group include compounds having a polymerizable group such as those represented by the following formulas (M-1) to (M-6). (3-3) In the case where a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group, a method for producing a liquid crystal display element may be employed, following the procedure described above in (3-1) and then a step of irradiating with ultraviolet light, as described below. This method, similar to the production of the PSA-type liquid crystal display element, allows for the production of a liquid crystal display element with excellent response speed with a low light exposure dose. The compound having a polymerizable group may be a compound having one or more polymerizable unsaturated groups, such as acrylate groups or methacrylate groups, in the molecule, as represented by the above formulas (M-1) to (M-6). The content of the compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of all polymer components. Furthermore, the polymerizable group may be contained in the polymer used in the liquid crystal aligning agent. Examples of such polymers include polymers obtained by reacting a diamine component containing a diamine having the above photopolymerizable group at its terminal.

[0076] (4) Step of Irradiating the Liquid Crystal Cell with Light The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above. The voltage applied here can be, for example, 5 to 50 V DC or AC. The light to be irradiated can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiation light can be, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, or an excimer laser. The light irradiation dose is preferably 1,000 to 200,000 J / m ２ and more preferably 1,000 to 100,000 J / m ２ is.

[0077] A liquid crystal display element can be obtained by laminating a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate to be laminated to the outer surface of the liquid crystal cell include a polarizing plate in which a polarizing film called an "H film" made by stretching and aligning polyvinyl alcohol and absorbing iodine is sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0078] The liquid crystal display element of the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, information displays, etc. In addition, the polymer composition contained in the liquid crystal aligning agent can be used as a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmissive / scattering liquid crystal dimming element, or for other applications such as a protective film for a color filter, a gate insulating film for a flexible display, or a substrate material.

[0079] The present invention will be specifically described below with reference to examples, but the present invention should not be construed as being limited to these examples. The abbreviations of the compounds and the methods for measuring the respective properties are as follows.

[0080] (Tetracarboxylic acid dianhydrides) (DC-1) to (DC-2): Compounds represented by the following formulas (DC-1) to (DC-2), respectively

[0081] (Diamine) (DA-1) to (DA-10): Compounds represented by the following formulas (DA-1) to (DA-10), respectively.

[0082] (Solvent) THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve [Viscosity] Measurement was performed using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL (milliliters), a cone rotor TE-1 (1°34', R24), and a temperature of 25°C. [Measurement of Molecular Weight] The molecular weights (number average molecular weights) of polyimide precursors, polyimides, etc. were measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.) and columns (GPC KD-803 and GPC KD-805 in series) (manufactured by Showa Denko K.K.) under the following conditions: Column temperature: 50°C Eluent: N,N-dimethylformamide (containing lithium bromide monohydrate (LiBr.H) as an additive). ２ o-Phosphoric acid) at 30 mmol / L, tetrahydrofuran (THF) at 10 mL / L. Flow rate: 1.0 mL / min. Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory Co., Ltd.).

[0083] <Evaluation of Refractive Index by Molecular Orbital Calculation> The refractive index of the following molecules (A) to (G) was evaluated by performing molecular orbital calculation.

[0084] Here, the refractive index can be calculated from the polarizability when the structure obtained by molecular orbital calculation for the target molecule is optimized, using the following calculation formula (1) (Lorentz-Lorenz formula). In the molecular orbital calculation for structural optimization, B3LYP was used as the functional and 6-31G* as the basis function. Furthermore, the refractive index was calculated as a value at 550 nm, and in this case, the UV spectrum was calculated using TD-B3LYP as the functional and 6-31G* as the basis function. In the molecular orbital calculation for structural optimization, it is possible to use, for example, Gaussian09 (Revision C.01, M.J. Frisch, et al., Gaussian, Inc., 2010.) manufactured by Gaussian, Inc., USA, as molecular orbital calculation software. However, the means for performing molecular orbital calculation is not limited to this. (n ２ −1) / (n ２ +2) = 4πα / 3V (1) (In the above formula (1), n ​​represents the refractive index, α represents the polarizability, and V represents the volume per monomer. V can be calculated using the following formula (2).) V = V ｖｄｗ / K ｐ ... (2) (In the above calculation formula (2), V ｖｄｗ is the molar volume of the monomer, K ｐ represents the filling factor (0.681).

[0085] The calculation results are shown in Table 1. As shown in Table 1, the molecules (A) to (C) derived from the specific diamines (DA-1) to (DA-3) exhibited higher refractive indices than the molecules (D) to (E) that did not have a triazine ring and the molecules (F) to (G) in which the side chain group bonded to the triazine ring was a polycyclic structure such as a long-chain alkyl group or cholesterol.

[0086] [Synthesis of specific diamines (DA-1) to (DA-3)] The synthesis methods of the compounds represented by formulae (DA-1) to (DA-3) are described in detail below. The compound represented by formula (DA-1) and the compound represented by formula (DA-3) are novel compounds that have not been published in literature.

[0087] < １H-NMR Measurement> Apparatus: Fourier transform superconducting nuclear magnetic resonance spectrometer (FT-NMR) "AVANCE III" (manufactured by BRUKER) 500 MHz. Solvent: deuterated dimethyl sulfoxide ([D ６ ]-DMSO, standard: tetramethylsilane), deuterated chloroform (CDCl ３ (Standard substance: tetramethylsilane) <Monomer Synthesis Example 1: Synthesis of (DA-1)> Diamine (DA-1) was synthesized according to the route shown below. Under a nitrogen atmosphere, 2,4-dichloro-6-methoxy-1,3,5-triazine (8.97 g, 49.8 mmol) and acetone (179 g) were added to a solution cooled to 0 ° C. in an ice bath. In a separate container, 4-nitrophenol (17.3 g, 124 mmol), acetone (138 g), and a 20% aqueous solution of sodium hydroxide (25.0 g) were added to form a homogeneous solution, and the solution cooled to 0 ° C. was added dropwise. After stirring for 1 hour, the temperature was raised to 50 ° C. and stirring was continued for 17 hours. After that, a 2% aqueous solution of sodium carbonate (400 g) was added, and crystals precipitated. The precipitated crystals were filtered, and the cake was washed twice with saturated aqueous sodium bicarbonate (45 g), twice with water (45 g), and twice with methanol (27 g), in that order. After drying in vacuo at 60 ° C., DA-1-1 (16.7 g, 43.3 mmol, yield 87.0%, white solid) was obtained. THF (314 g) and 5% palladium carbon (N.E. Chemcat Corporation, 50% by mass water content, 1.57 g) were added to DA-1-1 (15.7 g, 40.8 mmol), and nitro reduction was carried out at room temperature under a hydrogen atmosphere. After the reaction, the palladium carbon was filtered off, and the crude product obtained by concentrating the filtrate was recrystallized from isopropyl alcohol (96.0 g) to obtain DA-1 (10.1 g, 31.0 mmol, yield 76.1%, white solid). １ From the results of H-NMR, this solid was confirmed to be diamine (DA-1). １ H-NMR (500MHz, CDCl ３ ): δ (ppm) = 6.94 (d, 4H, J = 8.8Hz), 6.65 (d, 4H, J = 8.8Hz), 3.92 (s, 3H), 3.65 (br, 4H)

[0088] Monomer Synthesis Example 2: Synthesis of (DA-2) Diamine (DA-2) was synthesized according to the route shown below. A solution of 2,4-dichloro-6-methoxy-1,3,5-triazine (18.0 g, 100 mmol) dissolved in acetonitrile (216 g) was added dropwise over 40 minutes to a solution of paraphenylenediamine (86.5 g, 800 mmol) dissolved in methanol (396 g) heated to 60°C. After the dropwise addition was completed, the mixture was stirred at 60°C for 1 hour, and then triethylamine (25.3 g, 250 mmol) was added and stirred for 10 minutes, after which the solvent was distilled off. When 50°C water (306 g) was added to the solution (234 g) after distillation of the solvent, a solid precipitated. After cooling to room temperature, the precipitated solid was separated by filtration, and the resulting solid was cake-washed three times with a mixed solvent of water (72.0 g) and methanol (72.0 g) heated to 50°C. Acetonitrile (404 g) was added to the washed solid, and the solid was dissolved under reflux conditions, and insoluble components were removed by filtration. The obtained filtrate was concentrated, and methanol (100 g) was added to the crude product obtained, and the mixture was stirred for 1 hour under heating conditions at 60°C. After that, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration and dried in vacuo at 40°C to obtain DA-2 (14.9 g, 46.2 mmol, yield 46.2%, pink solid). The following １ From the results of H-NMR, this solid was confirmed to be diamine (DA-2). １ H-NMR (500MHz, [D ６ ]-DMSO): δ (ppm) = 9.13-9.10 (m, 2H), 7.28 (s, 4H), 6.48 (s, 4H), 4.80 (s, 4H), 3.81 (s, 3H)

[0089] Monomer Synthesis Example 3: Synthesis of (DA-3) Diamine (DA-3) was synthesized according to the route shown below. Acetone (125 g) was added to 2,4-dichloro-6-methoxy-1,3,5-triazine (12.5 g, 69.6 mmol), and the solution was cooled to 0°C. In a separate vessel, 4-aminothiophenol (19.2 g, 153 mmol), acetone (115 g), and a 20% by mass aqueous solution of sodium hydroxide (30.6 g) were added to form a homogeneous solution, and the solution cooled to 0°C was added dropwise. After stirring at 0°C for 3 hours, the reaction solution was recovered while removing the by-product sodium chloride by decantation, and the resulting solution was concentrated to obtain a crude product. Ethyl acetate (269 g) and water (168 g) were added to the obtained crude product, and the mixture was separated and washed. The resulting organic layer was heated to 78°C, and the insoluble by-product was removed by filtration. The ethyl acetate solution was then concentrated. Ethyl acetate (134 g) was added to the obtained slurry concentrate, and the slurry was stirred at room temperature for 1 hour. After that, the target product was collected by filtration and dried in vacuo at 40°C to obtain DA-3 (11.3 g, 31.6 mmol, yield 45.4%, light gray solid). １ From the results of H-NMR, this solid was confirmed to be diamine (DA-3). １ H-NMR (500MHz, [D ６ ]-DMSO): δ (ppm) = 7.12 (d, 4H, J = 8.6Hz), 6.58 (d, 4H, J = 8.6Hz), 5.54 (br, 4H), 3.69 (s, 3H)

[0090] [Synthesis of Polyamic Acid] <Synthesis Example 1> 1.46 g (4.50 mmol) of DA-1 and 2.08 g (10.5 mmol) of DA-5 as diamine components were weighed into a 50 mL four-neck flask equipped with a stirrer, and 24.8 g of NMP was added and stirred to dissolve. While stirring this diamine solution, 2.82 g (14.4 mmol) of DC-1 as a tetracarboxylic dianhydride component was added, and then 11.3 g of NMP was added, and the mixture was stirred at room temperature for 15 hours to obtain a solution of polyamic acid (A-1) (viscosity: 638 mPa s, number average molecular weight: 14,085).

[0091] Synthesis Examples 2 to 5 Solutions of polyamic acids (A-2) to (A-5) shown in Table 2 were obtained in the same manner as in Synthesis Example 1, except that the diamine component and the tetracarboxylic dianhydride component were changed to those shown in Table 2. The viscosities and molecular weights of the obtained polyamic acids are shown in Table 2.

[0092] [Preparation of liquid crystal aligning agent] <Example 1> NMP (6.0 g) and BCS (7.2 g) are added to the solution (4.8 g) of polyamic acid (A-1) obtained above, and stirred at room temperature for 10 hours, to obtain a liquid crystal aligning agent (PAA-1) in which the concentration of polyamic acid (A-1) in the liquid crystal aligning agent is 4 mass %, and the solvent composition ratio is NMP:BCS=56:40 (mass ratio).

[0093] Examples 2 to 3 and Comparative Examples 1 to 2 Liquid crystal aligning agents (PAA-2) to (PAA-5) shown in Table 3 were obtained by carrying out the same procedure as in Example 1, except that the polyamic acid solution was changed to that shown in Table 3. In the table, the "solid content concentration" represents the ratio of the content of the liquid crystal aligning agent other than the solvent component contained in the liquid crystal aligning agent to the entire liquid crystal aligning agent.

[0094] Examples 4 to 6 and Comparative Example 3 The liquid crystal aligning agent (PAA-1) obtained in Example 1 and the liquid crystal aligning agent (PAA-5) obtained in Comparative Example 2 were mixed so that the mass ratio of each was 3:7 (PAA-5:PAA-1), and the mixture was stirred at room temperature for 3 hours to prepare a liquid crystal aligning agent (PAA-b-1) of Example 4. In addition, the liquid crystal aligning agents (PAA-b-2) to (PAA-b-4) of Examples 5 to 6 and Comparative Example 3 shown in Table 4 below were prepared by carrying out the same procedure as in Example 4, except that the combination of liquid crystal aligning agents used was changed to that shown in Table 4 below.

[0095] [Measurement of Refractive Index of Liquid Crystal Alignment Film] The liquid crystal alignment agents prepared in Examples 1 to 3 and Comparative Example 1 were spin-coated onto a silicon wafer, dried on a hot plate at 70°C for 90 seconds, and then baked in a hot air circulating oven at 230°C for 20 minutes to form a liquid crystal alignment film with a thickness of 100 nm. Next, a spectroscopic ellipsometer M-2000 (manufactured by J.A. Woollam) was used to measure the refractive index at wavelengths of 250 to 800 nm using a CAUCHY model fitting. The results are shown in Table 5. Table 5 also lists the refractive index at a wavelength of 550 nm. As an evaluation standard, a refractive index of 1.630 or higher was rated "excellent," and a refractive index of less than 1.630 was rated "unacceptable."

[0096] [Measurement of Transmittance of Liquid Crystal Alignment Film] A measurement cell was prepared using two quartz substrates. The liquid crystal alignment agents prepared in Examples 1 to 3 and Comparative Example 1 were spin-coated onto the quartz substrates, dried on a hot plate at 70°C for 90 seconds, and then baked in a hot air circulating oven at 230°C for 20 minutes to form a 100 nm-thick liquid crystal alignment film. A quartz substrate without a liquid crystal alignment film was attached to the substrate, with the liquid crystal alignment film facing inward. A refractive index liquid (Shimadzu Device Mfg. Co., Ltd., Contact Liquid) was inserted between the substrates using a dropper to prepare a measurement cell. Eleven refractive index liquids were selected from 1.60 to 1.70 in 0.01 increments to match the respective refractive indices. The transmittance of the prepared measurement cell was measured at wavelengths of 380 to 800 nm using a UV-visible spectrophotometer (Shimadzu Corporation, UV-2600).

[0097] The results are shown in Table 5. Table 5 lists the average values ​​of transmittance in the wavelength range of 380 to 800 nm. As evaluation criteria, a transmittance of more than 99.90% was rated as "excellent," a transmittance of 99.90% or less but more than 99.0% was rated as "passable," and a transmittance of 99.0% or less was rated as "unacceptable."

[0098] As shown in Table 5, the liquid crystal alignment films obtained from the liquid crystal alignment agents using the specific diamines (DA-1) to (DA-3) exhibited a higher refractive index than the liquid crystal alignment films obtained from the liquid crystal alignment agents composed of diamine components not containing the specific diamines. In addition, the liquid crystal alignment films obtained from the liquid crystal alignment agents using the specific diamines (DA-1) to (DA-3) exhibited a high light transmittance.

[0099] [Preparation of Liquid Crystal Alignment Film and Liquid Crystal Cell] Liquid crystal cells were prepared as follows using the liquid crystal alignment agents prepared in Examples 4 to 6 and Comparative Example 3 above. Each liquid crystal alignment agent was spin-coated onto the ITO surface of an ITO electrode substrate on which an ITO electrode pattern with a pixel size of 100 μm x 300 μm and a line / space of 5 μm each was formed, dried on a hot plate at 70°C for 90 seconds, and then baked in a hot air circulating oven at 230°C for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm. The liquid crystal alignment agent was also spin-coated onto the ITO surface on which no electrode pattern was formed, dried on a hot plate at 70°C for 90 seconds, and then baked in a hot air circulating oven at 230°C for 20 minutes to form a liquid crystal alignment film with a thickness of 100 nm. For the two substrates described above, 4 μm bead spacers were sprayed onto the liquid crystal alignment film of one of the substrates, and then a sealant (Mitsui Chemicals, Inc., XN-1500T) was printed on top of them. Next, the other substrate was bonded to the previous substrate with the side on which the liquid crystal alignment film was formed facing inward, and the sealant was then thermally cured to prepare an empty cell. A liquid crystal containing a polymerizable compound for PSA (MLC-3023, manufactured by Merck, a negative liquid crystal) was injected into this empty cell by a reduced pressure injection method to prepare a liquid crystal cell. Then, with a DC voltage of 15 V applied to this liquid crystal cell, ultraviolet light was applied from the outside of the liquid crystal cell at 10 J / cm through a filter that cuts off wavelengths of 325 nm or less. ２ The illuminance of the ultraviolet light was measured using a UV-MO3A manufactured by ORC Corporation. Thereafter, in order to deactivate any unreacted polymerizable compound remaining in the liquid crystal cell, the liquid crystal cell was irradiated with ultraviolet light (UV lamp: FLR40SUV32 / A-1) for 30 minutes using a UV-FL irradiation device (manufactured by Toshiba Lighting & Technology Corporation) in the absence of applied voltage.

[0100] [Evaluation of vertical alignment] The evaluation of the vertical alignment of each liquid crystal cell prepared as described above is shown in Table 6. The evaluation method is as follows. Each liquid crystal cell was sandwiched between crossed Nicol polarizers, and with a backlight irradiated from the rear, the liquid crystal cell was rotated, and the change in brightness was visually observed to determine whether the liquid crystal was vertically aligned. The evaluation criteria were "Good" when the liquid crystal was vertically aligned, and "Poor" when the liquid crystal was not vertically aligned. The results are shown in Table 6. As shown in Table 6, the liquid crystal alignment films obtained from the liquid crystal aligning agents using the specific diamines (DA-1) to (DA-3) exhibited good vertical alignment properties.

[0101] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-37989, filed on March 10, 2021, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. The following formula (D Ｔ and polyimides which are imidized products of the polyimide precursors. 【Chemistry 1】 (In the formula, R represents a hydrogen atom, a hydroxyl group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms, * represents a bond, and any hydrogen atom of the benzene ring bonded to * may be replaced with a monovalent group, L １ and L ２ each independently represents a single bond, -(CH ２ ) ｎ -(n is an integer of 1 to 6), -NR'-, -(CH ２ ) ｎ represents -NR'- (n is an integer of 1 to 6), -O-, -S-, -O-CO-, or -CO-O-, and R' represents a hydrogen atom or a monovalent organic group.

2. The formula (D Ｔ The partial structure represented by the following formula (d Ｔ -1) to (d Ｔ The liquid crystal aligning agent according to claim 1, which is any one of the above-mentioned. 【Chemistry 2】 (In the formula, R and * are each represented by the formula (D Ｔ ) has the same meaning as R and *.

3. The diamine (0) is represented by the following formula (d ０ The liquid crystal aligning agent according to claim 1 or 2, which is a diamine represented by the formula: 【Chemistry 3】 (Formula (d ０ In the formula (D Ｔ Ar and Ar′ each independently represent a divalent aromatic ring group, and a hydrogen atom of the aromatic ring may be substituted with a monovalent group; L ｄ and L ｄ Each ' is independently a single bond, -(CH ２ ) ｎ -(n is an integer of 1 to 6), -NR'-, -(CH ２ ) ｎ represents -NR'- (n is an integer of 1 to 6), -O-, -S-, -O-CO-, or -CO-O-, where R' represents a hydrogen atom or a monovalent organic group; m and m′ are each independently an integer from 0 to 2; Ar, Ar', L ｄ and L ｄ When there are multiple Ar, Ar', L ｄ and L ｄ ' may be the same or different.)

4. The diamine (0) is represented by the following formula (d ０ -1) to (d ０ The liquid crystal aligning agent according to any one of claims 1 to 3, which is any diamine selected from the group consisting of: 【Chemistry 4】 (R is the above formula (D Ｔ ) has the same meaning as R in

5. The polymer (P) is obtained by a polymerization reaction of the diamine component and a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride represented by the following formula (T): 【Chemistry 5】 (In formula (T), X represents a structure selected from any one of the following formulas (x-1) to (x-13).) 【Chemistry 6】 (In the formula, R １ ~R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group; R ５ and R ６ each independently represents a hydrogen atom or a methyl group, j and k are integers of 0 or 1, １ and A ２ each independently represents a single bond, —O—, —CO—, —COO—, a phenylene group, a sulfonyl group, or an amide group, *1 represents a bond bonding to one acid anhydride group, *2 represents a bond bonding to the other acid anhydride group, and ２ may be the same or different.)

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

7. The liquid crystal alignment agent further includes, as other diamines, diamines represented by the following formula (d1) or (d2), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, diamines having a photoalignment group, diamines having a radical initiation function, diamines having a photopolymerizable group at the end, diamines represented by the following formulas (z-1) to (z-13), diamines represented by the following formulas (5-1) to (5-13), diamines represented by the following formulas (Ox-1) to (Ox-2), and at least one polymer selected from the group consisting of polyimide precursors and polyimides which are imidized products of the polyimide precursors obtained using diamine components containing the diamines, the liquid crystal alignment agent according to any one of claims 1 to 6. 【Chemistry 7】 (Wherein, X is a single bond, —O—, —C(CH ３ ) ２ -, -NH-, -CO-, -(CH ２ ) ｍ -, -SO ２ -, -O-(CH ２ ) ｍ -O-, -OC(CH ３ ) ２ --, --CO--(CH ２ ) ｍ -, -NH-(CH ２ ) ｍ -, -SO ２ - (CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -, -CONH-(CH ２ ) ｍ -NHCO- or -COO-(CH ２ ) ｍ represents --OCO--, m is an integer of 1 to 8, and Y represents a structure represented by any one of the following formulas (S1) to (S2), and in the above formula (d2), the two Y's may be the same or different. 【Chemistry 8】 (In formula (S1), X １ is a single bond, -(CH ２ ) ａ -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CO-N(CH ３ )-, -NH-, -O-, -COO-, -OCO- or -((CH ２ ) ａ１ -A １ ) ｍ１ - (a1 is an integer from 1 to 15, A １ represents an oxygen atom or -COO-; m １ is an integer from 1 to 2. １ When is 2, a plurality of a1 and A １ each independently has the same definition as above; G １ represents a divalent cyclic group selected from a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom; m is an integer of 1 to 4, and when m is 2 or more, a plurality of X １ , G １ are each independently defined as above, R １ represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, and * represents a bond.) 【Chemistry 9】 (In formula (S2), X ２ is -CONH-, -NHCO-, -O-, -CH ２ O-, -OCH ２ represents -, -COO- or -OCO-; ２ represents a structure having a steroid skeleton, at least one of the hydrogen atoms of the structure having a steroid skeleton is substituted with a substituent selected from the group consisting of a halogen atom, a halogen-atom-containing alkyl group, a halogen-atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group in which any carbon-carbon bond of the halogen-atom-containing alkyl group, halogen-atom-containing alkoxy group, alkyl group having 3 to 10 carbon atoms, alkoxy group having 3 to 10 carbon atoms, and alkenyl group having 3 to 10 carbon atoms is interrupted by an oxygen atom, and * represents a bond. 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】

8. The liquid crystal aligning agent according to claim 7, wherein the other diamine is a diamine represented by the formula (d1) or (d2).

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

11. A method for manufacturing a liquid crystal display device, comprising carrying out the following steps (1) to (3) in this order: Step (1): A step of applying the liquid crystal aligning agent according to any one of claims 1 to 8 onto at least one of a pair of substrates having a conductive film to form a coating film. Step (2): Baking the coating film Step (3): forming a liquid crystal layer between the pair of substrates to prepare a liquid crystal cell.

12. The method for producing a liquid crystal display element according to claim 11, further comprising the following step (4) after steps (1) to (3): Step (4): Irradiating the liquid crystal cell with light

13. The following formula (D ＴＳ ) is a diamine having a structure represented by the formula: 【Chemistry 14】 (Formula (D ＴＳ In the above, R represents a hydrogen atom, a hydroxyl group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms, and any hydrogen atom of the benzene ring bonded to the amino group may be replaced with a monovalent group.

14. Formula (D ＴＳ The structure represented by the following formula (d ０ -3), (d ０ -6) and (d ０ The diamine according to claim 13, which has a structure represented by any one of the following: 【Chemistry 15】 (wherein R is the same as the formula (D ＴＳ ) has the same meaning as R in

15. A polymer obtained from a diamine component comprising the diamine according to claim 13 or 14.

16. A polyimide precursor obtained by a polycondensation reaction between a diamine component containing the diamine according to claim 13 or 14 and a tetracarboxylic acid component, or an imidized product thereof.

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