TWI354843B - Liquid crystal alignment agent and liquid crystal - Google Patents

Description

1354843 IX. Description of the Invention: [Technical Field] The present invention relates to a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent capable of forming a liquid crystal alignment film having good electrical properties and excellent printability, and a liquid crystal display element containing the liquid crystal alignment film. [Prior Art] At present, as a liquid crystal display element, a TN type liquid crystal display element having a so-called TN (Twisted Nematic) type liquid crystal cell is known, which is formed of polylysine, polyfluorene on the surface of a substrate provided with a transparent conductive film. A liquid crystal alignment film formed of an imide or the like is used as a substrate for a liquid crystal display element, and the two substrates are opposed to each other, and a nematic liquid crystal layer having positive dielectric anisotropy is formed in the gap to form a sandwich structure. The unit cell, the long axis of the liquid crystal molecules is continuously twisted by 90 degrees from one substrate to the other substrate. Further, STN (Super Twisted Nematic) type liquid crystal display elements and vertical alignment type liquid crystal display elements having higher contrast and smaller viewing angle dependence than TN type liquid crystal display elements have been developed. The STN type liquid crystal display element uses a liquid crystal in which a chiral agent as an optically active substance is blended in a nematic liquid crystal as a liquid crystal by using a long axis of liquid crystal molecules to be continuously twisted by 180 degrees or more between substrates. The birefringence effect produced by the state. In contrast, as described in Non-Patent Document 1 and Patent Document 1, a vertical alignment type liquid crystal display element called an MVA method in which protrusions are formed on I TO to control the alignment direction of liquid crystals has been proposed. The liquid crystal display element of the V A type is excellent not only in viewing angle and contrast, but also in the process of forming the liquid crystal alignment film, and is also excellent in the process. As a liquid crystal alignment film suitable for the 1354843 ΤΝ, STN, and MVA systems, it is required that the residual image erasing time of the liquid crystal display element is short. Further, as an alignment agent for forming the liquid crystal alignment films, it is required to have excellent printability in lithography. [Non-Patent Document 1] "Liquid Crystal" Vol. 3 No. 2, 117 (Patent Document 1) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. It is a liquid crystal alignment agent which can form a liquid crystal alignment film which maintains a voltage holding ratio and reduces an accumulated electric charge, and has excellent printability, and a liquid crystal display element using the liquid crystal alignment film. Other objects and advantages of the invention will be apparent from the description which follows. According to the present invention, the above objects and advantages of the present invention are attained by a liquid crystal alignment agent characterized by containing a compound represented by the following formula (I) (hereinafter, also referred to as a specific compound).

(wherein R, R8 are each independently a hydrogen atom, an alkyl group or an alkoxy group, and R9 to R12 are each independently a hydrogen atom, an aromatic group or an aliphatic group, and A is a hydrogen atom or an aliphatic group. Group, η is an integer from 1 to 100). In the above formula (I), the following compounds are preferred compounds, and 1 to 118 1354843 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, R9. RI2 is a hydrogen atom, A is a hydrogen atom, and η is an integer of 1 to 100. In the above formula (I), the following compounds are other preferred compounds, and R, R8 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. , R9 and Rh are aromatic groups, R,. And R12 is a hydrogen atom or an aliphatic group, A is a hydrogen atom or an aliphatic group, and η is an integer of 1 to 1 Å. Further, in the above formula (I), the following compound is a more preferable compound, and each of R and R8 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. R9 and Ru are aromatic groups, Ri. And Riz is a hydrogen or an epoxy group-containing aliphatic group, A is a hydrogen atom or an epoxy group-containing aliphatic group, and η is an integer of from 1 to 100. According to the present invention, the above objects and advantages of the present invention, and secondly, are achieved by a liquid crystal alignment agent characterized in that R, R, R8 in the above formula (I) are each independently a hydrogen atom and have a carbon number of 1 to 1. 6 alkyl or an alkoxy group having 1 to 6 carbon atoms, R9 to Ru are each a hydrogen atom, A is a hydrogen atom, and η is an integer of 1 to 100, and the above preferred compound is reacted with tetracarboxylic acid dianhydride. Poly-proline polymer (hereinafter also referred to as a specific poly-proline polymer). Further, the liquid crystal alignment agent of the present invention may further contain at least one of the above specific compound and the above specific polyaminic acid polymer, and a polylysine composed of a repeating unit represented by the following formula (I-1) and At least 1354484 kinds of polymers selected from the group consisting of polyimine consisting of repeating units represented by (1-2) • (1-1) HOOC, COOH HNOC', CONH — Q1-

(wherein p2 is a tetravalent organic group, and Q2 is a divalent organic group). [Embodiment] Hereinafter, the present invention will be described in more detail. The liquid crystal alignment agent of the present invention is preferably constituted by dissolving at least one of a specific compound and a specific polyamic acid polymer and at least one polymer selected from the group consisting of polyamic acid and polyimine in an organic solvent. [Specific compound] In the formula (1), ' Ri to R8 are each independently a hydrogen atom, an alkyl group or an alkoxy group. The alkyl group and the alkoxy group are preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 1354843 carbon atoms. The alkyl group contained in such an alkyl group and an alkoxy group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a 2-methyl-propyl group or a 3-methyl group. Propyl, n-pentyl, n-hexyl. R9 to Rl2 are each independently a hydrogen atom, an aromatic group or an aliphatic group. Preferred are a hydrogen atom, a phenyl group, a naphthyl group, an aliphatic group having 1 to 4 carbon atoms or an aliphatic group having an epoxy group, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. , glycidyl group. A is preferably a hydrogen atom or an aliphatic group having 1 to 4 carbon atoms or an aliphatic group containing an epoxy group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a glycidyl group. Further, η is an integer of 1 to 100. Particularly preferably, Ri to Rs are hydrogen, and Rs to R12 are each independently a hydrogen atom, a methyl group, an ethyl group, a phenyl group or a glycidyl group, and A is a hydrogen atom or a glycidyl group. The following compounds are mentioned as a specific compound.

-10- 1354843

1354843

Among the above specific compounds, when r9 to r12 are each a hydrogen atom, a specific polyaminic acid polymer can be obtained by reacting it with an acid dianhydride. In the synthesis of the specific polyaminic acid polymer, as the acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,3-dimethyl-1 are preferable. 2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, -12- 1354843 1,3,3a,4,5,9b-hexahydro-5 -(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[1,2-c]furan-1,3-dione, cis-3,7-dibutylcyclooctane-1 , 5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3 ,33,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene[l,2-c]furan-1, 3-diketo' 3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2, 5-dioxotetrahydro-3-furanyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2 : 3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraketone, pyromellitic dianhydride, and the like. These acid dianhydrides may be used alone or in combination of two or more. Further, in this case, in addition to the above specific compound having a diamine structure, other diamine compounds may be used. Preferred examples of the other diamine compound include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, and 2,2'-dimethylene. 4--4'-diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminopurine, 9,9-dimethyl-2,7-diaminopurine, 4, 4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluorodecane, 4,4'-(p-phenylene) Isopropylidene)diphenylamine, 4,4'-(m-phenylene isopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-extension methyldi(cyclohexyl) Amine), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4- Diaminopyridine '2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N -ethyl-3,6-diaminocarbazole, -13- 1354843 N-phenyl-3,6-diaminocarbazole, N,N, bis(4.aminophenyl)·benzidine , Ν,Ν'-bis(4-aminophenyl) ) Ν Ν, Ν, - dimethyl-benzidine, and the like. These other -amine compounds may be used alone or in combination of two or more. [Polyuric acid] <tetracarboxylic dianhydride> In the present invention, the tetracarboxylic dianhydride used in the synthesis of the polyamic acid other than the specific polyaminic acid polymer is preferably Alicyclic tetracarboxylic acid dianhydride. Examples of the alicyclic tetracarboxylic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2·dimethyl-1,2,3,4-cyclobutane. Alkanetetracarboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,3-dichloro-1,2,3,4-cyclobutane Tetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid Anhydride, 1,2,4,5·cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexyltetracarboxylic dianhydride 'cis-3,7-dibutylcyclooctane -1,5-diene-1,2,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6-tricarbonyl-2-carboxyl group Borneol-2:3,5:6-dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic acid diacid liver, l,3,3a,4,5,9b-hexahydro-5- (four gas -2,5-dioxo-3-furanyl)naphthalene [l,2-c]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-5 -methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [l,2-c]-furan-1,3-dione, 1,3,3&,4 ,5,91)-hexahydro-5-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-indole [l,2-c]-furan-1,3 -di Ketone, l, 3, 3a, 4, 5, 9b - Hydrogen-7-methyl-5-(tetraki-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3, 3a,4,5,9b-hexahydro-7-ethyl-5-(tetrahydro-2,5-dioxo-3-furanyl)·14- 1354843 naphthalene [l,2-c]-furan -1,3-diketone, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [ 1,2-(:]-furan-1,3-dione, 1,3,33,4,5,91)-hexahydro-8-ethyl-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphthalene [1,2-c]-furan-1,3-dione, 1,3,3&,4,5,915-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2<]-furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran methylene) 3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3 -oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetra Hydrogen-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane - 2:3, 5:6 - dianhydride, 4,9-dioxatricyclo[5.3.1.0''6]undecane-3,5,8,10-tetraone, formula (II) below (III) a compound represented by

(wherein R1 and R3 represent a divalent organic group having an aromatic ring, R2 and R4 represent a hydrogen atom or an alkyl group, and each of R2 and R4 present in plural may be the same or different). -15- 1354843 Further, an aliphatic tetracarboxylic anhydride such as butane tetracarboxylic acid dianhydride; pyromellitic dianhydride; 3,3',4,4'-benzophenonetetracarboxylic acid diacid 3 may be mentioned. , 3', 4, 4'-diphenyltricarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ',4,4'-diphenyl ether tetracarboxylic anhydride, 3,3',4,4'-dimethyldiphenyldecane tetracarboxylic acid diacid 3,3',4,4'-tetraphenyl Decane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide diacid 4,4'-di (3,4-dicarboxyphenoxy)diphenylgonadoic anhydride, 4,4'(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4' - All-propylene dicarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, di(phthalic acid) a phenylate dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenylbenzoic acid)-4, 4'-diphenyl ether dianhydride, di(triphenylene) Tetraphthalic acid)-4,4'-based methane dianhydride, ethylene glycol-di(hydroper trimellitate), propylene glycol water trimellitate), 1,4-butanediol·di (dehydration) Trimellitic acid ester), 1 diol-di (dehydrated trimellitate), 1,8-octanediol-di(dehydrated phenyl ester), 2,2-bis(4-hydroxyphenyl)propane - an aromatic tetracarboxylic dianhydride such as a di(dehydrated trimellitate) or a compound represented by the following ~(4). They may be used alone or in combination of two or more. Carboxylic anhydride, diacid carboxylic anhydride, carboxylic acid anhydride, fluoroisophthalate phosphine oxide, m-dimethyldiphenyl bis(de, 6-hexanetricarboxylic acid) (1) to 1 -16 - 1354843

^CH3 ^CH3

(3)

Among the above tetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl- are preferable from the viewpoint of being able to exhibit good liquid crystal alignment properties. 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-17- 1354843-1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, 12,3,4-cyclopentanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 5-(2,5-dioxotetrahydrofuranmethylidene)-3-methyl- 3_cyclohexene-i,2-dicarboxylic acid dianhydride, cis-37-dibutylcyclooctane-1,5-diene-fluorene, 2,5,6-tetracarboxylic dianhydride, 3, 5,6-Tricarbonyl-2-carboxynorbornane-2:3,5:6-dianhydride, 1,3,3&,4,5,91)-hexahydro-5-(tetrahydro-2, 5-dioxo-3-furanyl)-naphthalene [1,2-(:]-furan-1,3-dione, 1,3,33,4,5,91>-hexahydro-8-A 5-5-(tetrahydro-2,5-dioxo-3-indolyl)-naphthalene [l,2-c]furan-1,3-dione, 1,3,33,4,5, 9 hexahydro-5,8-dimethyl-5-(tetrahydro-2,5-dioxo-3.furanyl)-naphthalene [uc]furan-1,3-dione, bicyclo[2.2. 2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo[32.1]octane-2,4-dione-6-spiro _3,-(tetrahydrofuran-2,5'-dione), 5·(2,5·dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2 - Diphthalic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclo[5.3.1.02.6]undecane _3,5,8,10-tetraketone, an alicyclic tetracarboxylic dianhydride of a compound represented by the following formulas (5) to (7) in the compound represented by the above formula (Π), and the above formula (III) An alicyclic tetracarboxylic dianhydride such as a compound represented by the following formula (8) in the compound to be represented, and particularly preferred is 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, l,3,3a,4,5, 9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanylnaphthalene [1,2-c]·furan-1,3-dione, cis-3,7-dibutyl Kecyclooctane-1,5-diene-1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2:3,5:6-di Anhydride, 1,3,3&,4,5,91)-hexahydro-8-methyl-5-(tetrahydro-2,5-di-18- 1354843 oxo-3-furanyl)-naphthalene l,2-c]furan-1,3-dione, 3-oxa double [3 octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-dioxotetrahydro-3-furanyl-3-methyl 3-cyclohexene-1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxynorbornane-2:3,5:6-dianhydride, 4,9-ditricyclo[5.3 .1.02·6] undecane-3,5,8,10-tetraketone, and a compound of the following formula (5). .2.1] (2,5-anhydride' oxo

Preferred tetracarboxylic acid dianhydrides other than the alicyclic tetracarboxylic acid dianhydride include, butane tetracarboxylic acid dianhydride pyromellitic dianhydride, 3, 3', 4, 4 '-benzophenone tetracarboxylic acid dianhydride, homo-anhydride, -19- 1354843 3,3',4,4'-biphenylfluorene tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyl Tetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, and the like. Among these tetracarboxylic acid dianhydrides, the alicyclic tetracarboxylic acid dianhydride is preferably 50 mol% or more based on the total tetracarboxylic acid dianhydride. <Diamine> Examples of the diamine used in the synthesis of the above polyamic acid other than the specific polyaminic acid polymer include p-phenylenediamine, m-phenylenediamine, and 4,4'-diamine. Diphenylmethane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl maple, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminobenzimidamide, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1-(4' -aminophenyl)-1,3,3-trimethylindan, 6-amino-1-(4'-aminophenyl)-1,3,3-trimethylindan, 3, 4'-Diaminodiphenyl ether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2 - bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-di(4 -aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl] maple, 1,4-bis(4-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy) Benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-aminophenyl)-10-hydroquinone, 2,7-diaminoguanidine, 9,9 -Dimethyl-2,7-diaminopurine, 9,9-bis(4-aminophenyl)anthracene, 4,4'-methyl-bis(2-chloroaniline), 2,2' ,5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3 , 3'-dimethoxy-4,4'-diaminobiphenyl, -20- 1354843 1,4,4'-(p-phenylphenylisopropylene)diphenylamine, 4,4' - (m-phenylene isopropylidene)diphenylamine, 2,2'-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4' -diamino-2,2'-bis(trifluoromethyl)biphenyl' 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl Aromatic diamine; 1,1-m-xylylenediamine, 1,3-propanediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, 4,4 -diaminoheptamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienyldiamine, hexahydro-4,7-methylene quinone dimethyl Diamine, tricyclo[6.2.1.02·7]-undecene dimethyl Aliphatic and alicyclic groups such as 4,4'-methyl bis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane, 1.4-bis(aminomethyl)cyclohexane Diamine; 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2.4-diaminopyrimidine, 5,6-diamino-2,3- Dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4- Bis(3-aminopropyl)pyridazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy- 1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2 , 4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2, 6-Diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino- 2-ethoxy acridine lactate, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopyridazine, 3,6-diaminoacridine, di(4- Aminophenyl)phenylamine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminoguanidine , N-phenyl-3,6-diaminocarbazole, hydrazine, Ν'- -21 - 1354843 bis(4-aminophenyl)-benzidine, anthracene, Ν'-bis(4-aminobenzene) a diamine having two first-order amine groups and a nitrogen atom other than the first-order amine group in a molecule such as N-N,N'-dimethyl-benzidine; and a diamine-based organic compound represented by the following formula (IV) Oxane and the like. These diamines may be used alone or in combination of two or more. R5 I HgN-^-CH^· Si-

(IV)

(In the formula, R5 represents a hydrocarbon group having 1 to 12 carbon atoms, and R5 each may be the same or different, p is an integer of 1 to 3, and q is an integer of 1 to 20; Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4,- are preferred. Diaminobiphenyl, 1,5-diaminonaphthalene, 2,7-diaminoguanidine, 9,9-dimethyl-2,7-diaminopurine, 4,4'-diaminodi Phenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-di[4-(4- Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylphenyldiisopropylidene)diphenylamine, 4,4'-(m-phenylene diisopropylidene)diphenylamine, 1,4-cyclohexanediamine, 4,4'-methyl bis(cyclohexylamine), 1,3-two (Aminomethyl) cyclohexane, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diamine Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6- Diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl) -benzidine and the like. -22- 1354843 &amp; When the liquid crystal alignment agent of the present invention has a pretilt performance performance, it is preferred that some or all of Q| and Q2 in the above formulas (I-1) and (I-2) are as follows: (Q-1) and at least one group represented by the following formula (Q-2). In other words, a diamine having a group represented by the following formula (Q-1) or the following formula (q-2) (hereinafter also referred to as ''specific diamine') is used. They may be used alone or in combination of two or more. Used in combination.

(wherein X is a single bond, -〇-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an aryl group, and R6 is a carbon number of 10 to 20 An alkyl group, a monovalent organic group having an alicyclic skeleton of 4 to 40 carbon atoms or a monovalent organic group having a fluorine atom of 6 to 20 carbon atoms).

(wherein X is a single bond, -0-, -CO·, -COO-, -OCO-, -NHCO-, -C0NH-, -S- or an aryl group, and R7 is a carbon number of 4 to 40. a divalent organic group having an alicyclic skeleton). In the above formula (Q-1), the alkyl group having 10 to 20 carbon atoms represented by R6 may, for example, be n-decyl, n-dodecyl, n-pentadecyl, n-hexadecyl or n. Octaalkyl, n-icosyl, and the like. In addition, as the organic group having an alicyclic skeleton having 4 to 40 carbon atoms represented by R6 of the above formula (Q-1) and R7 in the above formula (Q-2), for example, -23- 1354843 a group of an alicyclic skeleton of a cycloalkane such as an alkane, a cyclopentane, a cyclohexane or a cyclodecane; a group having a steroid skeleton such as cholesterol or cholestyl alcohol; having a norbornene; A group having a bridged alicyclic skeleton such as adamantane. Among them, a group having a steroid skeleton is particularly preferred. The organic group having the above alicyclic skeleton may also be a group substituted by a halogen atom (preferably a fluorine atom) or a fluoroalkyl group (preferably a trifluoromethyl group). Further, the fluorine atom-containing group having 6 to 20 carbon atoms represented by R6 in the above formula (Q-1) may, for example, be a straight chain having 6 or more carbon atoms such as n-hexyl group, n-octyl group or n-decyl group. An alkyl group; an alicyclic hydrocarbon group having 6 or more carbon atoms such as a cyclohexyl group or a cyclooctyl group; and a part or all of a hydrogen atom of an organic group such as an aromatic hydrocarbon group having 6 or more carbon atoms such as a phenyl group or a biphenyl group; a group substituted with a fluoroalkyl group such as an atom or a trifluoromethyl group. Further, 'X in the above formula (Q-1) and the above formula (Q-2) is a single bond, -〇- '-CO- ' -COO- ' -OCO- &gt; -NHC0- ' -CONH- ' or The aryl group, as the aryl group, may, for example, be a phenyl group, a tolyl group, a phenyl group, a naphthyl group or the like. Among them, a group represented by -0-, -COO-, -OCO- is particularly preferred. Specific examples of the diamine having a group represented by the above formula (Q-1) are preferably dodecyloxy-2,4·diaminobenzene and pentadecyloxy-2,4. -diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, a compound represented by the following formulas (9) to (13). •24- 1354843

(13) Further, as a specific example of the diamine having a group represented by the above formula (Q-2), preferred are diamines represented by the following formulas (14) to (16).

Among them, particularly preferred are compounds represented by the above formulas (9), (11), (13), and (14). -25- 1354843 The ratio of use of the specific diamine to the amount of all diamines varies depending on the magnitude of the pretilt angle to be expressed. For the case of TN type and STN type liquid crystal display elements, it is preferably 0 to 5 The molar % is preferably 5 to 1% by mole for the case of the vertical alignment type liquid crystal display element. &lt;Synthesis of Polyglycine&gt; The ratio of use of the tetracarboxylic dianhydride to the diamine for the synthesis reaction of poly-proline (including a specific poly-proline polymer) is preferably relative to 1 equivalent of the diamine. The amine group 'the acid anhydride group of the tetracarboxylic acid dianhydride is a ratio of 0.2 to 2 equivalents, more preferably 0.3 to 1.2 equivalents. The synthesis reaction of polylysine is preferably carried out in an organic solvent at a temperature of _2 (TC ～ 150 ° C, more preferably 〇 100 ° C. Here, 'as an organic solvent' as long as it can be dissolved The synthetic polyaminic acid is not particularly limited, and examples thereof include, for example, methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-butoxy Amidoxime solvent such as hydrazine, hydrazine-dimethylpropanamide, 3-methoxy hydrazine, hydrazine-dimethylpropionamide, 3-hexyloxy hydrazine, hydrazine-dimethylpropionamide , aprotic polar solvents such as dimethyl hydrazine, 7-butyrolactone, tetramethyl urea, hexamethylphosphonium triamine; phenolic solvents such as m-methylphenol, xylenol, phenol, halogenated phenol, etc. 1〜30重量百分比。 The total amount of the total amount of the tetracarboxylic acid dianhydride and the diamine compound (n) relative to the total amount of the reaction solution (α + Lu) is 0. 1~30% by weight In addition, in the range in which the produced polyamine acid is not precipitated, the organic solvent may also be a poor solvent of poly lysine, -26- 1354843, Examples, esters, acids, halogenated hydrocarbons, hydrocarbons, etc. Specific examples of such a poor solvent include methanol, ethanol, isopropanol, cyclohexanol, and 4-hydroxy-4-methyl-2. · Pentanone, ethylene glycol, propylene glycol, hydrazine, 4 · butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl Ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether , ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether 'ethylene glycol ether acetate, 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, tetrahydrofuran, dichloromethane, 1, 2_ dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexanthene, gypsum, xinyuan, benzene, toluene, xylene, isonic acid Isobutyric acid Ester, diisoamyl ether, etc. As described above, a reaction solution in which polyamic acid is dissolved is obtained. Then, the reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure. Or the reaction solution can be distilled off under reduced pressure with an evaporator to obtain a poly-proline acid, and the process of dissolving the poly-proline in an organic solvent once or several times, and then precipitating it with a poor solvent can be used. Refined polyaminic acid. <Dehydration ring closure reaction> The polyimine constituting the liquid crystal alignment agent of the present invention can be synthesized by dehydration ring closure of a part or all of the above polyamic acid. -27- 1354843 used in the present invention. The ratio of the repeating unit having a quinone ring in all repeating units of polyimine (hereinafter also referred to as "deuterated imidization ratio") is 40 mol% or more, preferably 50 mol% or more. By using a polymer having a ruthenium iodide ratio of 40 mol% or more, a liquid crystal alignment liquid crystal alignment agent capable of forming a afterimage erasing time can be obtained. The ruthenium amination rate can be determined by the following method. [Method for Measuring the Amidation Rate of the Iridium Amineated Polymer] The ruthenium iodide polymer is dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, based on tetramethyl decane. The substance was subjected to W-NMR measurement at room temperature. It is obtained by the formula expressed by the following formula (ii): 醯 imidization ratio (%) = (Ι—Α'/Α^α ) χ100----(ϋ) Α1: peak area of protons derived from sulfhydryl groups (l〇ppm) A2: peak area α derived from other protons: the ratio of the number of other protons in the precursor of the polymer (polyproline) to the proton of one NH matrix The dehydration ring closure is (i) a method of heating poly-proline, or (ii) a method of dissolving a polyhydrazide in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating as needed. And proceed. The reaction temperature in the method for heating poly-proline in the above (i) is preferably 50 to 20 ° C, more preferably 60 to 17 (TC. When the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction cannot be Completely, if the reaction temperature exceeds 200 ° C, the molecular weight of the obtained ruthenium-imided polymer may decrease. On the other hand, the dehydrating agent -28- is added to the poly-proline solution in the above (ii). In the method of 1354843 and the dehydration ring-closing catalyst, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride may be used as the dehydrating agent, and the dehydrating agent may be used depending on the desired imidization ratio, preferably relative to 1 mol. The agglutination repeating unit is 0.01 to 20 moles. Further, as the dehydration ring closure, for example, pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. However, it is not limited thereto. 1 The dehydrating agent used in the molar is preferably 0.01 to 1 Torr. The more the amount of the aqueous solvent and the dehydration ring-closing catalyst, the higher the quinone imine. Moreover, as the organic solvent used in the dehydration ring-closing reaction, Polyglycine The organic solvent is exemplified as the solvent used in the solvent, and the reaction temperature of the dehydration ring-closure reaction is preferably from 0 to 180 ° C, more preferably from 150 to C. Further, by subjecting the reaction solution thus obtained to the same operation as the acid purification method, The specific poly <end-modified type polymer which can be obtained by refining> The poly-proline and polyimine used in the present invention may also be a molecularly-modified terminal-modified polymer. By using the terminal polymer, The coating property and the like of the liquid agent can be improved without impairing the effects of the present invention. The terminal-modified polymer can be added to the reaction system by adding a monobasic acid anhydride, a monoisocyanate compound, etc., to the reaction system. And synthesis. Among them, 'as a unitary one, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-benzoic anhydride, n-dodecyl succinic anhydride, n-tetradecyl citrate cetyl succinic anhydride, etc. Further, as the monoamine compound, for example, an amount of a deuterated acid, such as a deuterated acid, may be used in a three-stage amount, and the above-mentioned deuteration ratio is more likely to be mentioned. Preferably, it is a 10-mer amide compound. Modified crystals were passed over the polyamine anhydride, decyl succinic anhydride, by way of example -29- 1354843 such as aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, positive Indoleamine, n-decylamine, n-undecylamine, n-dodecylamine, trialkylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-alkylamine, n-octadecylamine Further, as the monoisoester ester compound, for example, phenyl isocyanate or naphthyl isocyanate [solution viscosity], the polymer used in the alignment agent of the present invention, at 10% In the case of a solution, it preferably has a viscosity of 20 to 800 mPa's, more preferably a viscosity of 500 mPa's. In addition, using a specific solvent, for a solution diluted to a specific solid concentration, an E-type rotational viscometer is used in 2 The viscosity of the polymer solution (mPa's) was measured at 5 °C. [Liquid crystal alignment agent] The liquid crystal alignment agent of the present invention is usually composed of a specific compound or a polyglycolic acid polymer, preferably the above polymer, and optionally added components, which are dissolved in an organic solvent. The liquid crystal alignment agent of the present invention may further contain a cyclic compound or a functional decane-containing compound from the viewpoint of improving the adhesion to the surface of the substrate without impairing the physical properties of the object. Examples of such epoxidation include ethylene glycol diglycidyl ether 'polyethylene glycol di-distillate, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, diol diglycidyl ether, and neopentyl Alcohol diglycidyl ether, 1&gt;6-hexane diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol II, ortho-cyanate cyanate 3 0~ composition melting Poly-integrated, oxy-property, glycerol-polypropyl alcohol dihydrate -30- 1354843 glyceryl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, hydrazine, hydrazine, Ν' four Glycidyl-m-xylylenediamine, 1,3-bis(indole, fluorene-di-glycidylmethyl)cyclohexane, hydrazine, hydrazine, Ν', Ν'-tetraglycidyl group 4,4 '-Diphenylmethane, 3-(Ν-allyl-indole-glycidyl)aminopropyl decane, 3-(anthracene, Ν-diglycidyl)aminopropyltrimethoxyanthracene, Ν-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl-amine cyclohexanthes and the like. Further, as the epoxy group-containing compound, preferred are, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol glyceryl ether, and neopentyl Glycol diglycidyl ether, 1,6-hexanediol dicondensate, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycid 1,3,5,6-tetraglycidyl- 2,4-hexanediol, ^^,-tetrakilyl-m-xylylenediamine, 1,3-bis(indole, fluorene-diglycidylamino) hexane, hydrazine, hydrazine, hydrazine , Ν' · tetraglycidyl-4,4'-diaminodiazane, hydrazine, hydrazine-diglycidyl-benzylamine, hydrazine, hydrazine-diglycidyl ylcyclohexane, etc. These include The blending ratio of the epoxy group compound is preferably 40 parts by weight or less, more preferably 0.1 parts by weight, based on the part by weight of the polymer. Examples of the functional decane-containing compound include propyltrimethoxydecane. 3-aminopropyltriethoxydecane, 2.-trimethoxydecane, 2-aminopropyltriethoxydecane, N-(2-yl)-3-aminopropyltrimethoxydecane, N-(2-Aminoethyl)-3-aminomethyl Methoxydecane, 3-ureidopropyltrimethoxydecane, 3, anthracene, -oleylamine diaminotrimethoxydecane, methyl group to exemplify propylene glycol diglycidyl ether, oleyl ether, glycidylmethyl benzene Methyl-aminomethyl if at 100~30 heavy 3·amino-aminopropyl-aminoethyl propyl-ureidopropyl-31 - 1354843-based triethoxydecane 'N-ethoxycarbonyl-3 Aminopropyltrimethoxydecane, Ν-ethoxycarbonyl-3-aminopropyltriethoxydecane, N-triethoxydecylpropyltriethylamine, tris-trimethoxydecane Propyl triethylamine, 10-dimethoxydecyl-1,4,7-triazadecane, ι〇·triethoxyindolyl-1,4,7-triazole Heteroane, 9-trimethoxydecyl-3,6-diazadecyl acetate, 9-triethoxydecyl-3,6-diazadecyl acetate, Ν-section 3-aminopropyltrimethoxydecane, Ν·benzyl·3_aminopropyltriethoxydecane, Ν-phenyl-3-aminopropyltrimethoxy sane, Ν-benzene _3_Aminopropyltriethoxydecane, Ν-bis(oxyvinyl)-3-aminopropyltrimethoxy sulphane, N-di Oxyethylene) -3-aminopropyl triethoxy silane-like. The compounding ratio of the functional decane-containing compound is preferably 4 parts by weight or less based on 1 part by weight of the polymer. Examples of the organic solvent constituting the liquid crystal alignment agent of the present invention include 1-methyl-2-pyrrolidone, r·butyrolactone, r-butyrolactam, and ν,ν-dimethylformamidine. Amine, hydrazine, hydrazine-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, Ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether , ethylene glycol ethyl ether acetate, diglyme, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, 3-butoxy-indole, hydrazine-dimethylpropanamide, 3-methoxy-hydrazine, hydrazine-dimethylpropanamide, 3-hexyloxy-oxime, hydrazine-dimethyl Propionamide 'isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, and the like. Its -32-

In 1-354843, 3-butoxy-N,N-dimethylpropanamide, 3-methoxy-N,N-decylamine, 3-hexyloxy-N,N-dimethylpropionamide is shown Good and excellent. The solid content concentration in the liquid crystal alignment agent of the present invention is selected in consideration of viscosity or the like, and is preferably in the range of 1 to wt%. The liquid crystal alignment agent of the present invention is applied to the surface of the substrate to form a coating film for the film. When the solid content concentration is less than 1% by weight, the thickness of the film is too small, so that a good liquid crystal alignment film component concentration of more than 10% cannot be obtained. When % is used, the coating film thickness is too high to obtain a favorable liquid crystal alignment film, and the coating characteristics of the liquid crystal alignment agent are deteriorated. Further, a particularly preferable solid content concentration range differs depending on the method used in the case of the base phase alignment agent. For example, when it is a spin, it is preferably in the range of 1.5 to 4.5% by weight. When the printing method is used, the body component concentration is in the range of 3 to 9 % by weight, so that it can be kept in the range of 12 to 50 mPai. When the ink jet method is used, the concentration of the component is in the range of 1 to 5 wt%, so that the range of 3 to 15 mPa, s is dissolved. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably 〇 ° C or more preferably from 20 ° C to 60 ° C. &lt;Liquid crystal display element&gt; A liquid crystal display element obtained by using the liquid crystal alignment agent of the present invention is produced, for example, by the following method. - Printability of dimethyl propyl acrylate, volatilization I said that the coating is caused by liquid crystal alignment; when it is solid, it does not increase its density; when applying liquid crystal: method, Tetejia is the viscosity of the solution; For the solid i viscosity falling at ~200 〇C, the liquid crystal alignment agent of the present invention can be applied to the transparent layer formed by patterning by lithography, spin coating or inkjet printing. On one side of the substrate of the conductive film, 'subsequent' is formed by heating the coated surface to form a coating film. Here, as the substrate, for example, glass such as float glass or soda lime glass; polyethylene terephthalate 'polybutylene terephthalate, polyether oxime, polycarbonate, and alicyclic poly A transparent substrate made of plastic such as olefin. As the transparent conductive film provided on one surface of the substrate, a tin oxide film (NSA film made of SnO〇 (registered trademark of American PPG Co., Ltd.) and indium oxide-tin oxide (In2〇3 — Sn〇2) can be used. ITO film, etc. The pattern of these transparent conductive films is formed by photolithography or a mask in advance. In order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film during the application of the liquid crystal alignment agent, Further, a functional decane-containing compound, a functional titanium-containing compound, or the like may be applied to the surface of the substrate. After the liquid crystal alignment agent is applied, it is preferably carried out for the purpose of preventing the applied alignment agent liquid from sagging or the like. Preheating (pre-bake). The prebaking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, particularly preferably 40 to loot: » then, completely remove the solvent, in order to make the poly For the purpose of hydrazine imidization, a calcination (post-bake) process is carried out. The calcination (post-baking) temperature is preferably from 80 to 300 ° C, more preferably from 120 to 250 ° C. , the liquid of the invention containing polylysine The coating agent removes the organic solvent by coating to form a coating film as an alignment film, and further dehydrates and closes the film by further heating to form a coating film which is further imidized. The thickness of the formed coating film is preferably 0.001 to lvm, more preferably 0.005 to 0.5/zm. -34- 1354843 (2) The formed coating film surface is made of a roller wrapped with a cloth made of fibers such as nylon, rayon, cotton or the like. In the case of the liquid crystal alignment film in which the alignment property of the liquid crystal molecules is generated on the coating film, the liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention is disclosed, for example, in Japanese Laid-Open Patent Publication No. Hei 6-222366. Or a process of partially irradiating ultraviolet rays to change a pretilt angle as shown in Japanese Laid-Open Patent Publication No. Hei 6-281937, or performing a liquid crystal alignment after performing a sanding process as shown in Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. A protective film is partially formed on the surface of the film, and after being polished in a direction different from the previous polishing process, the protective film is removed, and the liquid crystal alignment of the liquid crystal alignment film can be changed. The treatment can improve the visual field characteristics of the liquid crystal display device. (3) Two substrates on which the liquid crystal alignment film is formed are formed, and the two substrates are placed opposite each other with a gap (cell gap ') to polish the respective liquid crystal alignment films. The directions are perpendicular or anti-parallel to each other, and the peripheral portions of the two substrates are bonded together with a sealant, and the liquid crystal is filled into the cell gap separated from the surface of the substrate and the sealant, and the injection holes are closed to form a liquid crystal cell. Then, On the outer surface of the liquid crystal cell, that is, on the other side surface of each of the substrates constituting the liquid crystal cell, the polarizer is bonded so that the polarizing direction thereof coincides with or perpendicular to the rubbing direction of the liquid crystal alignment film formed on one side of the substrate, thereby obtaining a liquid crystal. Display component. Here, as the sealant, for example, an alumina ball-containing epoxy resin or the like which is a curing agent and a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a disk-shaped liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an oxidized -35-1354843 azo liquid crystal, or a biphenyl liquid crystal can be used. A phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, a biphenylcyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal or the like. Further, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl phthalate, and cholesteryl carbonate may be added to these liquid crystals, and the trade names "C-1 5" and "CB-15" (manufactured by Merck & Co., Inc.) may be added. The chiral agent sold, etc. is used. Further, a ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate φ acid ester can also be used. In addition, the polarizing film to be bonded to the outer surface of the liquid crystal may be a polarizing film called a ruthenium film obtained by absorbing iodine while extending the alignment of the polyvinyl alcohol, and the polarizing film is formed by sandwiching the cellulose acetate protective film. A polarizer made of a film or a film itself. [Examples] Hereinafter, the present invention will be more specifically described by way of Examples, but the present invention is not limited to these Examples. • [Printability evaluation] A 127 mm (D) x 127 mm (W) Xl.lmm (H) glass substrate on which the enamel film was formed on one side was prepared, and the liquid crystal alignment agent obtained in the above experiment was passed through a pore diameter of 0.2. After filtering through a micropore filter of μιη, it was applied to a transparent electrode surface of the glass substrate by a liquid crystal alignment film coating printing machine (manufactured by Nippon Photo Printing Co., Ltd., Angstromer S-40L). The film was dried by a hot plate preheater set at 80 ° C, and baked at 200 ° C for 60 minutes to form a liquid crystal alignment film on a glass substrate with an ITO film. The unevenness of the obtained alignment film was visually evaluated according to the following criteria according to -36 to 1354843. 〇: No unevenness was observed at all. « △: Some sentences are observed. X: Unevenness was clearly observed. [Voltage Retention Rate] The liquid crystal display element was given at 60 ° C in a time interval of 1 67 msec; {5 V voltage was applied to the cow, the voltage application time was 60 μsec, and then the voltage was released from the voltage release to 167 msec. Voltage retention rate. The measuring device used VHR-1 manufactured by Dongyang Science and Technology Co., Ltd. [After image experiment] A unit cell with an ITO electrode as shown in Fig. 1 was produced. A DC voltage of 6.0 V was applied to the electrode A for 24 hours at room temperature, and a DC voltage of 0.5 V was applied to the electrode B for 24 hours. After releasing the stress, the electrodes a and b are nv

The gradient is applied with a DC voltage of 0.1 to 5.0 volts. The afterimage characteristics were judged by the difference in luminance between the electrodes a and B at the respective voltages. When the luminance difference is large, the afterimage characteristic is judged to be poor. 〇: No difference in brightness was found. △: There is a certain difference in brightness. &lt;Synthesis of a specific compound -37- 1354843 Catalyst h2nO~〇-nh2 A-l The nickel catalyst used in the reaction is easily deactivated by reaction with oxygen and water vapor in the atmosphere. Therefore, the solvent and the reagent used in the reaction are removed by pre-distillation and recrystallization to remove impurities. The polymerization was carried out under a nitrogen atmosphere. The polymerization was carried out according to the literature method (T. Kanbara, J. Polym. Sci. Part-A, Polym. Chem., 38, 4 194 (2000)). To a four-necked flask ventilated with nitrogen, 4,4'-dichlorobiphenyl (1 mmol), benzidine (1 mmol) and 15 ml of toluene were added. After stirring for a few minutes, a 3-stage butoxide was added at room temperature. Base sodium 288 mg (3 mmol), bis(1,5-cyclooctanedione) nickel (0) (Ni(cod) 2) 28 mg (0.1 mmol) and 1,1,-bis(diphenylphosphine) ferrocene Iron (DPPF) 166 mg (〇. 3 mmol). The reaction solution was heated to 60 ° C while stirring under a nitrogen atmosphere to start the reaction. After reacting at 60 ° C for 24 hours, 'a small amount of benzidine (0.05 mmol) was added, and the polymer terminal was blocked with benzidine' to terminate the polymerization. After cooling to room temperature, the reaction solution was poured into a mixed solution of 200 ml of aqueous ammonia and methanol, and the resulting precipitate was filtered off, and the recovered precipitate was further washed with methanol and diethyl ether to give the compound A-1. &lt;Synthesis of a specific compound 2&gt; -38- 1354843

A-2 The specific compound A_2 includes various structures as shown above. A solution of the specific compound A_1 in THF was mixed with an excess of sodium amine in a three-necked flask. After the solution was heated to reflux for 2 hours, the reaction solution was cooled to drop an excess of epibromohydrin. Heat to 80 ° C and continue stirring for 6 hours. The reaction solution was filtered, and the filtrate was washed with chloroform / 1 (%) aqueous hydrochloric acid and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was evaporated. The residue was reprecipitated with methanol to give the specific compound A-2. Polyimine synthesis example 1 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic dianhydride li2g (0.50 mol) and 1,3,3&amp;, 4,5,91)- Hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphthalene [1,2-(:]furan-1,3-dione 157 g (0.50 mol) ''p-phenylenediamine as a diamine compound 96g (0.89 mol), 3,3'-(tetramethyldioxanthene-13-diyl) bis(propylamine) 25g (〇.1() Mo Ear) and 3,6-bis(4-aminobenzimidyloxy)cholestane i3g (0.020 mol), n-octadecylamine as a -39-1354843 monoamine 8.1 g (0.030 mol) Dissolved in 960g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 6 hours. The obtained polyamidamine solution was divided into small amounts, added with NMP, and determined under a solid concentration of 1% by weight. The viscosity was 60 mPas. Next, 2700 g of N-methyl-2-pyrrolidone was added to the obtained polyamic acid solution, and 396 g of pyridine and 409 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. After the reaction, the solvent in the system is replaced with a new r-butyrolactone (by this operation, the oxime is imidized) The pyridine and acetic anhydride used in the reaction are removed to the outside of the system to obtain a solid concentration of 15% by weight and a solid concentration of 10% (r-butyrolactone solution). The solution viscosity is 70 mPa's, and the sulfhydrylation rate is 醯. About 95% of the ruthenium iodide polymer (as a "polyimine (a-1)") solution. Polyimine synthesis example 2 2,3,5-tricarboxyl group as tetracarboxylic dianhydride 224 g (1.0 mol) of cyclopentyl acetic acid dianhydride, p-phenylenediamine i 〇 gg (1 〇 mol) as a diamine compound and 7.8 g of 3,5-diaminobenzoic acid cholesteryl ester ( (K015 Moer) was dissolved in 3039 g of N-methyl-2-pyrrolidone and allowed to react at 60 ° C for 6 hours to obtain a polyamic acid solution having a solution viscosity of about 260 mPa·s. 2700 g of N-methyl-2-pyrrolidone was added to the polyaminic acid solution, 396 g of pyridinium and 306 g of acetic anhydride were added, and the mixture was dehydrated and closed for 4 hours at 1 TC. After the hydrazine imidization reaction, the solvent in the system was The new r-butyrolactone is subjected to solvent replacement (by this operation, the pyridine and acetic anhydride used in the oxime imidization reaction are removed to the outside of the system) to obtain about 3,000 g of solid. When the concentration of the body component is about 9.0 wt%, the concentration of the solid component is 10% (r-butyrolactone solution), the solution viscosity is -40 - 1354843 250 mPas, and the yttrium imidization polymer is about 5 i%. Brewed Fee polymer (a-2)") solution. Polylysine Synthesis Example 1 196 g (1.0 mol) of 12,3,4-cyclobutanetetracarboxylic acid dianhydride as a tetracarboxylic acid dianhydride, as a diamine compound of 2,2,-dimethyl- 4,4,·diaminobiphenyl 212g (l. oxime) is dissolved in 37〇g N_methyl-2-pyrrolidone, 3 3〇〇g of r-butyrolactone, so that it is at 4〇〇 The reaction was carried out for 3 hours at c to obtain a solution of polylysine having a solution viscosity of 160 mPa·s (as a "poly-proline (b-oxime)") solution of about 3 700 g. Polylysine Synthesis Example 2 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as tetracarboxylic acid dianhydride 95 g (0.50 mol), pyromellitic dianhydride i 〇 9 g (〇5) 2,7-diamino 芴 196 £ (1.0 mol) as a diamine compound dissolved in 23 〇£1^-methyl-2-pyrrolidone, 2060 g of r-butyrolactone In the reaction, the reaction was carried out at 4 ° C for 3 hours to add 1 3 50 g of r · butyrolactone to obtain a polyamic acid having a solution concentration of 125 mPa's at a solid concentration of 1 〇% (as The "polyglycine (b-2)") solution was about 3600 g. Example 1 Polyimine (a _ 1) prepared in Polyimine Synthesis Example 1 and polylysine (b-1) obtained in Polyamine Synthesis Example 1 were constructed as polyfluorene Imine: Polyamine: 20:80 (by weight) dissolved in r-butyrolactone/N-methyl-2-pyrrolidone/butyl cellosolve mixed solvent (weight ratio 71/1 7/12). To the solution, 2 parts by weight of -41 - 1354843 Ν, Ν, Ν', N'-tetraglycidyl-4,4'-diaminodiphenylmethane were further added to 100 parts by weight of the above polymer, respectively. 10 parts by weight of the specific compound A-1 was added to 100 parts by weight of the above polymer to prepare a solution having a solid concentration of 3.5% by weight and a 6.0% by weight solution. After the respective solutions were thoroughly stirred, they were filtered through a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent of the present invention. A solution having a solid concentration of 3.5% by weight in the above liquid crystal alignment agent was applied onto a transparent conductive film made of an ITO film provided on one surface of a glass substrate having a thickness of 1 mm using a spin coater (rotation speed: 2,500 rpm, coating time: After 1 minute), it was dried at 200 ° C for 1 hour to form a film having a dry film thickness of 〇.〇8 am. The film was subjected to a sanding treatment using a sanding machine equipped with a roll of rayon-made cloth, at a roll speed of 400 rpm, a table moving speed of 3 cm/sec, and a fluffing length of 0.4 mm. The above liquid crystal alignment film-coated substrate was ultrasonically washed in ultrapure water for 1 minute, and then dried in a clean oven at 100 ° C for 10 minutes. Then, on each of the outer edges of the liquid crystal alignment film of the liquid crystal alignment film coating substrate of the pair of transparent electrode/transparent electrode substrates, an epoxy resin adhesive to which an alumina ball having a diameter of 5. is applied is applied, and then The liquid crystal alignment film surface is relatively recombined and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-622 1 manufactured by Merck & Co., Inc.) is filled between the substrates through a liquid crystal injection port, and then the liquid crystal injection port is closed with an acrylic photocurable adhesive, and polarized light is applied to both sides of the substrate. The board is made of a TN liquid crystal display element. The voltage holding ratio evaluation and the afterimage evaluation of the obtained liquid crystal display element were carried out in accordance with the method described above. Further, using a solution having a solid concentration of 6.0% by weight, the printability was evaluated in accordance with the method described in -42 to 1354843. Examples 2 to 4 were carried out in the same manner as in Example 1 except that the polyimine, the polyamic acid, and the specific compound were used as shown in Table 1. Example 5 Polyimine (a-2) prepared in Polyimine Synthesis Example 2 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone/butyl cellosolve (weight ratio 50/50) Wherein φ is added to 2 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane relative to 100 parts by weight of the polymer, relative to 100 parts by weight of the polymer. 10 parts by weight of the specific compound A-1 was prepared as a solution having a solid concentration of 3.5% by weight and a solution of 6.0% by weight. After the respective solutions were thoroughly stirred, they were filtered through a filter having a pore size of 1 m to prepare a liquid crystal alignment agent of the present invention. The method for producing a liquid crystal display device, the method for evaluating a liquid crystal display device, and the method for evaluating the printability of an alignment agent were carried out in the same manner as in Example 1. • Example 6 The procedure was the same as in Example 5 except that the specific compounds were used in the materials shown in Table 1. Comparative Examples 1 to 2 The same procedures as in Example 1 were carried out except that the materials shown in Table 1 were used for the polyimine and polyamic acid without adding a specific compound. Comparative Example 3 - 43 - 1354843 The procedure was the same as in Example 5 except that no specific compound was added. Comparative Examples 4 to 5 The same procedures as in Example 1 were carried out except that the materials shown in Table 1 were used as the polyimine and polylysine, and the compound (compound X) having the following structure was used instead of the specific compound. Compound X is synthesized according to the method described in JP-A No. 2,446-8 3

Compound X Comparative Example 6 The same procedure as in Example 5 was carried out except that Compound X was added instead of the specific compound. Comparative Examples 7 to 8 The same procedures as in Example 1 were carried out except that the materials shown in Table 1 were used for the polyimine and the polyamine, and the compound (compound Y) having the following structure was used instead of the specific compound. . Compound γ was synthesized according to the method described in WO 2002/100949. Its molecular weight Mn = 15000, Mw = 30000 » Comparative Example 9 The same procedure as in Example 5 was carried out except that the compound γ was added instead of the specific compound. -44- 1354843

Table 1 Polyimine polyimine specific compound voltage retention rate afterimage printing Example 1 a-1 b-1 specific compound A-1 &gt; 99% 〇〇 Example 2 a-1 b-1 specific compound A-2 &gt; 99% 〇〇 Example 3 a-1 b-2 Specific compound A-1 &gt; 99% 〇〇 Example 4 a-1 b-2 Specific compound A-2 &gt; 99% 〇〇Implementation Example 5 a-2 - Specific Compound A-1 &gt; 99% 〇〇 Example 6 a-2 - Specific Compound A-2 &gt; 99% 〇〇 Comparative Example 1 a-1 b-1 4πτ ιΜΤ: &gt;99 % Δ 〇 Comparative Example 2 a-1 b-2 Μ &gt;99% △ 〇Comparative Example 3 a-2 — Μ /m &gt;99% Δ 〇Comparative Example 4 a-1 b-1 Compound X 98% Δ 〇 Comparative Example 5 a-1 b-2 Compound X 98% Δ 〇 Comparative Example 6 a-2 - Compound X 98% Δ 〇 Comparative Example 7 a-1 b-1 Compound Y 98% 〇X Comparative Example 8 a-1 b -2 Compound Y 98% 〇X Comparative Example 9 a-2 - Compound Y 98% 〇X [Simplified description of the drawing] Fig. 1 shows a unit cell with an ITO electrode prepared by evaluation of the residual image test. [Main component symbol description] Μ . /\\\ -45-

Claims (1)

1354843 X. Patent application scope: 1. A liquid crystal alignment agent' characterized by containing a compound represented by the following formula (1), (wherein, Ri to R8 are each independently a hydrogen atom, a group or an aristocratic group, and R9 to Ru are each independently a hydrogen atom, an aromatic group or an aliphatic group. A is a hydrogen atom or an aliphatic group. , η is an integer of 1 to 1 )). 2 _ The liquid crystal alignment agent of claim 1, wherein in the formula (I), r, R8 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon number of 1 to 6 The oxy group, R;»~Ri2 are each a nitrogen atom, A is a nitrogen atom, and η is an integer of from 1 to 100. 3. The liquid crystal alignment agent of claim 1, wherein R, R to R8 in the formula (I) are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; The oxy group, R9 and R&quot; are aromatic groups, Ri 〇 and Ru are hydrogen atoms or aliphatic groups, A is a hydrogen atom or an aliphatic group, and η is an integer of from 1 to 100. 4. The liquid crystal alignment agent of the first aspect of the invention, wherein R1 to Rs in the formula (1) are each independently a hydrogen atom, an alkyl group having a carbon number of 丨6 or an alkoxy group having a carbon number of 1 to 6, R9 and Rm are aromatic groups 'Ri. And the hydrogen atom or the epoxy group-containing aliphatic group 'A' is a hydrogen atom or an epoxy group-containing aliphatic group, and η is an integer of 1 to 1 Å. -46- 1354843 5. A liquid crystal alignment agent comprising a polyphthalic acid polymer obtained by reacting a compound of the second aspect of the patent application with a tetracarboxylic acid dianhydride. 6. The liquid crystal alignment agent according to any one of claims 1 to 5, further comprising a polylysine composed of a repeating unit represented by the following formula (I-1) and having the following formula ( I-2) at least one polymer selected from the group consisting of polyimine composed of repeating units, HOOQ ΌΟΟΗ (X -4- hnoc conh-q1- medium 团基-机N- has /===================================================================================================== 'In the liquid, one of the liquids and one of the special planes of the Bufan group, please use the price of 2, so that there is a Q to the liquid crystal solution, and the agent to the liquid crystal item 1 No. 6 to I . Perimembrane -47-